[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

TWI396700B - Transition metal compound, olefin polymerization catalyst and process for producing olefin polymer - Google Patents

Transition metal compound, olefin polymerization catalyst and process for producing olefin polymer Download PDF

Info

Publication number
TWI396700B
TWI396700B TW095118610A TW95118610A TWI396700B TW I396700 B TWI396700 B TW I396700B TW 095118610 A TW095118610 A TW 095118610A TW 95118610 A TW95118610 A TW 95118610A TW I396700 B TWI396700 B TW I396700B
Authority
TW
Taiwan
Prior art keywords
group
zirconium dichloride
butyl
fluorenyl
tert
Prior art date
Application number
TW095118610A
Other languages
Chinese (zh)
Other versions
TW200708531A (en
Inventor
Munehito Funaya
Koji Endo
Naritoshi Hirota
Yuichi Yamamura
Koji Kawai
Original Assignee
Mitsui Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Publication of TW200708531A publication Critical patent/TW200708531A/en
Application granted granted Critical
Publication of TWI396700B publication Critical patent/TWI396700B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

過渡金屬化合物，烯烴聚合用觸媒及烯烴系聚合體之製造方法Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer

本發明關於一種可有效作為烯烴聚合用觸媒成分且具有新穎的特定構造之過渡金屬化合物，於該過渡金屬化合物之製造中有用之中間體，含有該過渡金屬化合物之烯烴聚合用觸媒，以及使用該聚合用觸媒的烯烴系聚合體之製造方法。The present invention relates to a transition metal compound which is effective as a catalyst component for olefin polymerization and which has a novel specific structure, an intermediate useful in the production of the transition metal compound, a catalyst for olefin polymerization containing the transition metal compound, and A method for producing an olefin-based polymer using the catalyst for polymerization.

近年，作為烯烴聚合用之均勻系觸媒，可知有二茂金屬化合物。使用該二茂金屬化合物聚合烯烴之方法，特別是立體規則性地聚合α－烯烴之方法，自W.Kaminsky等人報告有整規聚合(Angew.Chem.Int.Ed.Engl.,24,507(1985))以來，已被廣為研究。In recent years, as a homogeneous catalyst for olefin polymerization, a metallocene compound is known. A method of polymerizing an olefin using the metallocene compound, particularly a method of stereoregulating an α-olefin, is reported from W. Kaminsky et al. (Angew. Chem. Int. Ed. Engl., 24, 507 (1985). )) has been widely studied.

已知於使用該二茂金屬化合物之α－烯烴聚合中，將取代基導入至二茂金屬化合物之配位基之環戊二烯基環上，或者使2個環戊二烯基環交聯，藉此大幅改變所得之α－烯烴聚合體之立體規則性或分子量。It is known that in the polymerization of an α-olefin using the metallocene compound, a substituent is introduced to a cyclopentadienyl ring of a ligand of a metallocene compound, or two cyclopentadienyl rings are crosslinked. Thereby, the stereoregularity or molecular weight of the obtained α-olefin polymer is largely changed.

例如，揭示有於丙烯之聚合觸媒中使用具有環戊二烯基環與茀基環所交聯之配位基的二茂金屬化合物之情形時，由立體規則性之觀面而言，可藉二甲基亞甲基(環戊二烯基)(茀基)二氯化鋯獲得間規聚丙烯(J.Am.Chem.Soc.,110,6255(1988))，藉於環戊二烯基環之3位上導入有甲基之二甲基亞甲基(3－甲基環戊二烯基)(茀基)二氯化鋯獲得半整規(hemiisotactic)聚丙烯(日本專利特開平3－193796)，同樣地藉導入了第三丁基之二甲基亞甲基(3－第三丁基－環戊二烯基)(茀基)二氯化鋯獲得整規聚丙烯(日本專利特開平6－122718)。又，揭示有經由二甲基亞甲基(3－第三丁基－5－甲基環戊二烯基)(茀基)二氯化鋯，於茀環之3,6位上導入第三丁基之二甲基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基茀基)二氯化鋯者，將得到整規立體規則性經提高的聚丙烯(WO01/27124)。For example, when a dimetallocene compound having a ligand having a cyclopentadienyl ring and a fluorenyl ring crosslinked is used in a polymerization catalyst for propylene, it can be considered from the viewpoint of stereoregularity. Syndiotactic polypropylene is obtained by dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (J. Am. Chem. Soc., 110, 6255 (1988)), by cyclopentane A methyl dimethylmethylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride is introduced at the 3-position of the alkenyl ring to obtain a hemiisotactic polypropylene (Japanese Patent) Kaiping 3-193796), similarly by introducing a third butyl dimethylmethylene (3-tert-butyl-cyclopentadienyl) (fluorenyl) zirconium dichloride to obtain a uniform polypropylene ( Japanese Patent Laid-Open No. 6-122218). Further, it is disclosed that dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride is introduced into the third and third positions of the anthracene ring. Butyl dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylindenyl) zirconium dichloride, will be obtained The stereoregularity of the improved polypropylene (WO 01/27124).

又，由分子量之觀點而言，已報告有：經由二甲基亞甲基(環戊二烯基)(茀基)二氯化鋯，將環戊二烯基環與茀環之交聯部改變為二苯基亞甲基交聯之二苯基亞甲基(環戊二烯基)(茀基)二氯化鋯者將獲得高分子量之間規聚丙烯(日本專利特開平2－274703)；經由二甲基亞甲基(3－(2－金剛烷基)－環戊二烯基)(茀基)二氯化鋯，使交聯部改變為二苯基亞甲基交聯之二苯基亞甲基(3－(2－金剛烷基)－環戊二烯基)(茀基)二氯化鋯者，將獲得高分子量之整規－半整規聚丙烯(Organometallics,21,934(2002))；經由二甲基亞甲基(3－第三丁基－環戊二烯基)(茀基)二氯化鋯，於環戊二烯基環之5位導入甲基之二甲基亞甲基(3－第三丁基－5－甲基環戊二烯基)(茀基)二氯化鋯者，將獲得高分子量之整規聚丙烯(日本專利特表2001－526730)。Further, from the viewpoint of molecular weight, it has been reported that a crosslinked portion of a cyclopentadienyl ring and an anthracene ring is via dimethylmethylene (cyclopentadienyl)(fluorenyl)zirconium dichloride. A diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride cross-linked to diphenylmethylene will be obtained as a high molecular weight syndiotactic polypropylene (Japanese Patent Laid-Open No. 2-274703) ); changing the cross-linking moiety to diphenylmethylene cross-linking via dimethylmethylene (3-(2-adamantyl)-cyclopentadienyl) (fluorenyl) zirconium dichloride Diphenylmethylene (3-(2-adamantyl)-cyclopentadienyl) (fluorenyl) zirconium dichloride, which will obtain high molecular weight stipulated semi-uniform polypropylene (Organometallics, 21,934) (2002)); introducing a methyl group at the 5-position of the cyclopentadienyl ring via dimethylmethylene (3-tert-butyl-cyclopentadienyl)(fluorenyl)zirconium dichloride Methylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, which will obtain high molecular weight conventional polypropylene (Japanese Patent Special Table 2001-526730) ).

進而，揭示有：藉於環戊二烯基環相鄰2個位置上導入取代基之二甲基亞甲基(3－第三丁基－2－甲基環戊二烯基)(茀基)二氯化鋯或二苯基亞甲基(3,4－二甲基環戊二烯基)(茀基)二氯化鋯，分別較二甲基亞甲基(3－第三丁基－5－甲基環戊二烯基)(茀基)二氯化鋯、二苯基亞甲基(3－甲基環戊二烯基)(茀基)二氯化鋯，獲得低分子量之聚丙烯(日本專利特表2001－526730、特開平10－226694)。Further, it is disclosed that a dimethylmethylene group (3-t-butyl-2-methylcyclopentadienyl group) is introduced by introducing a substituent at two positions adjacent to the cyclopentadienyl ring. Zirconium dichloride or diphenylmethylene (3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, respectively, compared to dimethylmethylene (3-tert-butyl -5-Methylcyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene (3-methylcyclopentadienyl)(fluorenyl)zirconium dichloride, obtaining low molecular weight Polypropylene (Japanese Patent Laid-Open No. 2001-526730, JP-A-10-226694).

如此，關於含有環戊二烯基環與茀環所交聯之配位基的二茂金屬化合物已有許多報告例。另一方面，報告例對於茀環3,6位之取代基種類係極端地限定。具體而言，已知於茀環3,6位上取代第三丁基之二茂金屬化合物，或茀環之2,3－位、6,7－位形成飽和6員環之二茂金屬化合(WO01/27124)，但均無任何具有於3,6－上取代不飽和鍵結之茀環的二茂金屬化合物之合成．聚合之報告例。此外，亦無關於在3,6位上取代碳－碳不飽和鍵結之茀衍生物的合成報告例。因此無法知曉此種二茂金屬化合物具有何等之性能。Thus, there have been many reported examples of metallocene compounds containing a ligand in which a cyclopentadienyl ring and an anthracene ring are crosslinked. On the other hand, the report example is extremely limited to the substituent type of the 3, 6 position of the anthracene ring. Specifically, it is known that a metallocene compound of a third butyl group is substituted at the 3, 6 position of the anthracene ring, or a 2,3-position, 6 or 7-position of the anthracene ring forms a saturated 6-membered ring metallocene compound. (WO01/27124), but none of them have any synthesis of a metallocene compound having an anthracene ring substituted with an unsaturated bond at 3,6-. Report example of aggregation. Further, there is no report on the synthesis of an anthracene derivative in which a carbon-carbon unsaturated bond is substituted at the 3,6 position. Therefore, it is impossible to know what properties such a metallocene compound has.

一般而言，由聚合活性、立體規則性或分子量等之方面而言，業者期望進一步改良使用該等二茂金屬化合物之聚合用觸媒。In general, from the viewpoints of polymerization activity, stereoregularity, molecular weight, and the like, it is desired to further improve the polymerization catalyst using these metallocene compounds.

又，另一方面，茀化合物近年來亦使用於有機電致發光元件等中，製造於3,6－上取代不飽和鍵結之茀亦有助於該等領域。On the other hand, ruthenium compounds have been used in organic electroluminescence devices and the like in recent years, and the production of 3,6-substituted unsaturated bonds has also contributed to such fields.

專利文獻1：日本專利特開平3－193796號公報專利文獻2：日本專利特開平6－122718號公報專利文獻3：WO01/27124專利文獻4：日本專利特開平2－274703號公報專利文獻5：日本專利特表2001－526730號公報專利文獻6：日本專利特開平10－226694號公報Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2001-526730, Patent Document 6: Japanese Patent Laid-Open No. Hei 10-226694

非專利文獻1：Angew.Chem.Int.Ed.Engl.,24,507(1985)非專利文獻2：J.Am.Chem.Soc.,110,6255(1988)非專利文獻3：Organometallics,21,934(2002)Non-Patent Document 1: Angew. Chem. Int. Ed. Engl., 24, 507 (1985) Non-Patent Document 2: J. Am. Chem. Soc., 110, 6255 (1988) Non-Patent Document 3: Organometallics, 21, 934 (2002) )

本發明之目的在於提供一種可有效作為有機電致發光元件或烯烴聚合用過渡金屬化合物之中間體的新穎茀化合物，以及作為烯烴聚合用觸媒成分之具有該茀環作為部分結構之過渡金屬化合物，含該過渡金屬化合物之烯烴聚合用觸媒，以及使用該觸媒製造烯烴系聚合體的方法。An object of the present invention is to provide a novel ruthenium compound which can be effectively used as an intermediate of an organic electroluminescence device or a transition metal compound for olefin polymerization, and a transition metal compound having the oxime ring as a partial structure as a catalyst component for olefin polymerization. A catalyst for olefin polymerization containing the transition metal compound, and a method for producing an olefin polymer using the catalyst.

本發明係用於解決上述問題者，發現藉由在3,6位上取代不飽和鍵結之茀化合物、具有含該茀之配位基之有用且新穎的過渡金屬化合物、含有該過渡金屬化合物之烯烴聚合用觸媒、以及使用該聚合用觸媒之烯烴系聚合體的製造方法，將達成本發明目的，並基於此而完成本發明。本發明之茀、以及過渡金屬化合物係分別為下述通式[I]以及[Ⅱ]所表示之過渡金屬化合物。The present invention is for solving the above problems, and finds a useful and novel transition metal compound having an unsaturated bond at the 3,6 position, a transition metal compound having a ligand containing the ruthenium, and a transition metal compound The catalyst for olefin polymerization and the method for producing an olefin polymer using the catalyst for polymerization achieve the object of the present invention, and the present invention has been completed based thereon. The oxime and the transition metal compound of the present invention are each a transition metal compound represented by the following general formulas [I] and [II].

[a]：一種茀衍生物，其特徵在於如下述通式[I]所示。[a]: an anthracene derivative characterized by the following formula [I].

(式中，R1 、R2 、R3 、R5 、R6 、R7 、R8 、R9 、R1 0 、R1 1 、R1 2 、R1 4 係選自氫、烴基、含矽基，且可分別相同亦可不同。R4 、R1 3 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，且可分別相同亦可不同。R1 至R1 4 之相鄰接之取代基亦可相互鍵結形成環。又，R4 與R5 可成為一體形成2價－Ra－，R1 2 與R1 3 亦可成為一體形成2價－Rb－。Ra、Rb為選自烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基之除了伸乙烯基以外之2價取代基。) (wherein R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 1 0 , R 1 1 , R 1 2 , R 1 4 are selected from hydrogen, a hydrocarbon group, Containing a fluorenyl group, and may be the same or different. R 4 and R 1 3 are selected from the group consisting of hydrogen, a hydrocarbon group, a sulfhydryl group, a sulfur-containing group, an oxy group, a nitrogen-containing group, a halogen-containing group, and may be the same respectively. The adjacent substituents of R 1 to R 1 4 may be bonded to each other to form a ring. Further, R 4 and R 5 may be integrated to form a divalent-Ra-, and R 1 2 and R 1 3 may also be used. The monovalent-Rb- is formed integrally. Ra and Rb are divalent substituents other than a vinyl group selected from a hydrocarbon group, a mercapto group, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, and a halogen-containing group.

[b]：如[a]之茀衍生物，其中，上述通式[I]中，R1 、R2 為氫。[b]: An anthracene derivative according to [a], wherein, in the above formula [I], R 1 and R 2 are hydrogen.

[c]：如[b]之茀衍生物，其中，上述通式[I]中，R1 、R2 、R3 、R8 、R9 、R1 4 為氫。[c]: an anthracene derivative according to [b], wherein, in the above formula [I], R 1 , R 2 , R 3 , R 8 , R 9 and R 1 4 are hydrogen.

[d]：如[c]之茀衍生物，其中，上述通式[I]中，R1 、R2 、R3 、R8 、R9 、R1 4 為氫，R4 與R5 及/或R1 2 與R1 3 係相互鍵結形成環。[d]: an anthracene derivative according to [c], wherein, in the above formula [I], R 1 , R 2 , R 3 , R 8 , R 9 and R 1 4 are hydrogen, R 4 and R 5 and / or R 1 2 and R 1 3 are bonded to each other to form a ring.

[e]：如[d]之茀衍生物，其中，上述通式[I]中，R1 、R2 、R3 、R8 、R9 、R1 4 為氫，R4 與R5 及/或R1 2 與R1 3 係相互鍵結形成5或6員環。[e]: an anthracene derivative according to [d], wherein, in the above formula [I], R 1 , R 2 , R 3 , R 8 , R 9 and R 1 4 are hydrogen, R 4 and R 5 and / or R 1 2 and R 1 3 are bonded to each other to form a 5 or 6 membered ring.

[f]：如[e]之茀衍生物，其如下述通式[Ⅱ]所示。[f]: an anthracene derivative such as [e], which is represented by the following formula [II].

(式中，R1 5 、R1 6 、R1 7 、R1 8 、R1 9 、R2 0 、R2 1 、R2 2 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，可分別相同亦可不同。) (wherein R 1 5 , R 1 6 , R 1 7 , R 1 8 , R 1 9 , R 2 0 , R 2 1 , R 2 2 are selected from the group consisting of hydrogen, a hydrocarbon group, a mercapto group, a sulfur-containing group, The oxygen-containing, nitrogen-containing, and halogen-containing groups may be the same or different.)

[g]：如[f]之茀衍生物，其中，上述通式[Ⅱ]中，R1 5 、R1 6 、R1 8 、R1 9 、R2 1 、R2 2 為甲基，R1 7 、R2 0 為氫原子。[g]: an anthracene derivative according to [f], wherein, in the above formula [II], R 1 5 , R 1 6 , R 1 8 , R 1 9 , R 2 1 and R 2 2 are a methyl group. R 1 7 and R 2 0 are a hydrogen atom.

[h]：一種過渡金屬化合物，其特徵為如下述通式[Ⅲ]所示。[h]: a transition metal compound characterized by the following formula [III].

(式中，R2 3 、R2 4 、R2 5 、R2 6 、R2 7 、R2 8 係選自氫、烴基、含矽基，可分別相同亦可不同，R2 3 至R2 8 之相鄰接之取代基亦可相互鍵結形成環。M為第4族過渡金屬，Y為碳原子，Q為可自鹵素、烴基、陰離子配位基或可以孤立電子對配位之中性配位基選擇相同或不同之組合，j為1~4之整數。Z為自通式[I]所表示之上述[a]~[e]之茀衍生物去除R1 、R2 所衍生之具有2價游離原子價的亞茀基，或去除2個[f]或者[g]所揭示之茀衍生物之10位之氫原子而衍生之具有2價游離原子價之亞茀基。再者，本發明中「茀衍生物之10位」係表示下述模式圖中之以＊表示之位置。模式圖中，省略茀骨架中超過雙重波線之周邊部化學鍵結之記載。) (wherein R 2 3 , R 2 4 , R 2 5 , R 2 6 , R 2 7 , and R 2 8 are selected from the group consisting of hydrogen, a hydrocarbon group, and a fluorenyl group, and may be the same or different, and R 2 3 to R The adjacent substituents of 2 8 may also be bonded to each other to form a ring. M is a transition metal of Group 4, Y is a carbon atom, and Q is a halogen, a hydrocarbon group, an anionic ligand or an ortho-electron pair. The neutral ligands are selected in the same or different combinations, and j is an integer from 1 to 4. Z is a radical derivative of the above [a] to [e] represented by the general formula [I], and R 1 and R 2 are removed. An anthracene group having a divalent free valence derived from a fluorenylene group having a divalent free valence of 2 or a dehydration of a hydrogen atom at the 10 position of the fluorene derivative disclosed in [f] or [g]. In the present invention, the "10-position of an anthracene derivative" means a position indicated by * in the following schematic diagram. In the schematic diagram, the description of the chemical bonding of the peripheral portion exceeding the double-wave line in the skeleton is omitted.

[i]：如[h]之過渡金屬化合物，其中，上述通式[Ⅲ]中，R2 4 、R2 6 為氫。[i]: a transition metal compound according to [h], wherein, in the above formula [III], R 2 4 and R 2 6 are hydrogen.

[j]：一種烯烴聚合用觸媒，其特徵為含有[h]或[i]任一項之過渡金屬化合物。[j]: A catalyst for olefin polymerization, characterized by containing a transition metal compound of any one of [h] or [i].

[k]：一種烯烴聚合用觸媒，其特徵為至少含有一種自以下選擇之化合物：(A)[h]或[i]任一項之過渡金屬化合物、與(B)(B－1)有機金屬化合物、(B－2)有機鋁氧化物化合物、(B－3)與過渡金屬化合物(A)反應形成離子對之化合物。[k]: a catalyst for olefin polymerization, characterized by containing at least one compound selected from the group consisting of a transition metal compound of any one of (A) [h] or [i], and (B) (B-1) The organometallic compound, the (B-2) organoaluminum oxide compound, and (B-3) are reacted with the transition metal compound (A) to form an ion pair compound.

[l]：一種烯烴系聚合體之製造方法，其係於[j]或[k]之烯烴聚合用觸媒存在下，使選自乙烯以及α－烯烴之1種以上之單體聚合的方法，其特徵為，至少1種單體為乙烯或丙烯。[1] A method for producing an olefin-based polymer, which comprises polymerizing one or more monomers selected from the group consisting of ethylene and an α-olefin in the presence of a catalyst for olefin polymerization of [j] or [k] It is characterized in that at least one monomer is ethylene or propylene.

[m]：如[l]之烯烴系聚合體之製造方法，其中，上述通式[Ⅱ]所表示之過渡金屬化合物係以載持於支持體上之形態使用。[M] The method for producing an olefin-based polymer according to the above [1], wherein the transition metal compound represented by the above formula [II] is used in a form supported on a support.

本發明提供一種藉由使用新穎茀衍生物、以及含有該衍生物之過渡金屬化合物(二茂金屬化合物)、含有該過渡金屬化合物之烯烴聚合用觸媒，而依非常高之活性製造有用之烯烴系聚合體的方法。The present invention provides a olefin which is produced by a very high activity by using a novel anthracene derivative, a transition metal compound (metallocene compound) containing the derivative, and a catalyst for olefin polymerization containing the transition metal compound. A method of polymerizing.

以下，依序說明：上述通式[I]所表示之茀衍生物，上述通式[Ⅲ]所表示之過渡金屬化合物，較佳的茀衍生物之例示，較佳的過渡金屬化合物之例示，本發明之茀衍生物的製造方法，本發明之過渡金屬化合物的製造方法，將本發明之過渡金屬化合物供給於烯烴聚合用觸媒時之較佳形態，繼而最後於含有本發明之過渡金屬化合物的烯烴聚合用觸媒之存在下製造烯烴系聚合體之方法。Hereinafter, the anthracene derivative represented by the above formula [I], the transition metal compound represented by the above formula [III], the preferred anthracene derivative, and the preferred transition metal compound are exemplified. The method for producing an anthracene derivative of the present invention, the method for producing a transition metal compound of the present invention, the preferred embodiment of the transition metal compound of the present invention when supplied to a catalyst for olefin polymerization, and finally to the transition metal compound of the present invention A method for producing an olefin-based polymer in the presence of a catalyst for olefin polymerization.

<茀衍生物><茀 derivative>

本發明之茀衍生物係以上述通式[I]表示。通式[I]中R1 、R2 、R3 、R5 、R6 、R7 、R8 、R9 、R1 0 、R1 1 、R1 2 、R1 4 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，可分別相同亦可不同。作為上述烴基，可列舉甲基、乙基、正丙基、烯丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基等直鏈狀烴基；異丙基、第三丁基、戊基、3－甲基戊基、1,1－二乙基丙基、1,1－二甲基丁基、1－甲基－1－丙基丁基、1,1－丙基丁基、1,1－二甲基－2－甲基丙基、1－甲基－1－異丙基－2－甲基丙基等支鏈狀烴基；環戊基、環己基、環庚基、環辛基、降基、金剛烷基、甲基環己基、甲基金剛烷基等環狀飽和烴基；苯基、甲苯基、萘基、聯苯基、菲基、蒽基等環狀不飽和烴基；苄基、異丙苯基、1,1－二苯基乙基、三苯基甲基等環狀不飽和烴基所取代之飽和烴基等。作為含氧基可列舉甲氧基、乙氧基、苯氧基、呋喃基等。作為含氮基可列舉N－甲基胺基、N,N－二甲基胺基、N－苯基胺基、比林基(pyryl)等。作為含硫基可列舉甲硫基、噻吩基等。作為含矽基，可列舉三甲基矽烷基、三乙基矽烷基、二甲基苯基矽烷基、二苯基甲基矽烷基、三苯基矽烷基等。作為含鹵素基可列舉氟原子、三氟甲基、2,2,2－三氟乙基、氟苯基、二氟苯基、三氟苯基、五氟苯基、三氟甲基苯基、雙(三氟甲基)等含氟基，氯原子、三氯甲基、2,2,2－三氯乙基、氯苯基、二氯苯基、三氯苯基、五氯苯基、三氯甲基苯基、雙(三氯甲基)等含氯基，溴原子、溴化苯基等含溴基，碘原子、碘苯基等含碘基等。The anthracene derivative of the present invention is represented by the above formula [I]. In the general formula [I], R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 1 0 , R 1 1 , R 1 2 and R 1 4 are selected from hydrogen, The hydrocarbon group, the mercapto group, the sulfur-containing group, the oxygen-containing group, the nitrogen-containing group, and the halogen-containing group may be the same or different. Examples of the hydrocarbon group include a linear chain such as a methyl group, an ethyl group, a n-propyl group, an allyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, a n-decyl group or a n-decyl group. Hydrocarbyl; isopropyl, tert-butyl, pentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propyl a branched hydrocarbon group such as butyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl or 1-methyl-1-isopropyl-2-methylpropyl; Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, descending a cyclic saturated hydrocarbon group such as an adamantyl group, a methylcyclohexyl group or a methyladamantyl group; a cyclic unsaturated hydrocarbon group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group or a fluorenyl group; a benzyl group; a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group such as cumyl, 1,1-diphenylethyl or triphenylmethyl. Examples of the oxygen-containing group include a methoxy group, an ethoxy group, a phenoxy group, a furyl group and the like. Examples of the nitrogen-containing group include an N-methylamino group, an N,N-dimethylamino group, an N-phenylamino group, and a pyryl group. Examples of the sulfur-containing group include a methylthio group, a thienyl group and the like. Examples of the fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a dimethylphenyl decyl group, a diphenylmethyl decyl group, and a triphenyl decyl group. Examples of the halogen-containing group include a fluorine atom, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a pentafluorophenyl group, and a trifluoromethylphenyl group. Fluorinated group such as bis(trifluoromethyl), chlorine atom, trichloromethyl, 2,2,2-trichloroethyl, chlorophenyl, dichlorophenyl, trichlorophenyl, pentachlorophenyl a chlorine-containing group such as trichloromethylphenyl or bis(trichloromethyl); a bromine-containing group such as a bromine atom or a phenyl bromide; an iodine-containing group such as an iodine atom or an iodophenyl group; and the like.

通式[I]中，較佳的是R1 、R2 、R3 、R5 、R6 、R7 、R8 、R9 、R1 0 、R1 1 、R1 2 、R1 4 為氫、碳數1~20之烴基、含有碳數0~20之含矽基、含硫基、含氧基、含氮基、含鹵素基。作為碳數1~20之烴基、含有碳數0~20之含矽基、含硫基、含氧基、含氮基、含鹵素基，可例示上述之取代基。In the formula [I], R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 1 0 , R 1 1 , R 1 2 , R 1 4 are preferred. It is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a mercapto group having a carbon number of 0 to 20, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, and a halogen-containing group. The above-mentioned substituents can be exemplified as the hydrocarbon group having 1 to 20 carbon atoms, the mercapto group having a carbon number of 0 to 20, the sulfur-containing group, the oxygen-containing group, the nitrogen-containing group, and the halogen-containing group.

又，R1 至R1 4 之相鄰接之取代基可相互鍵結形成環，亦可與接續該等之原子一同形成碳數1~20之亦可含有氧原子、氮原子、硫原子之環。又，R4 與R5 係可成為一體形成2價取代基之Ra，R1 2 與R1 3 亦可成為一體形成2價取代基之Rb。Ra、Rb為除了伸乙烯基以外之2價取代基，較佳為碳數1~20之烴基、含有碳數0~20之含矽基、含硫基、含氧基、含氮基、含鹵素基。作為上述2價烴基之例，可列舉亞甲基、伸乙基、亞乙基、伸丙基、亞異丙基、二甲基伸乙基、三甲基伸乙基、四甲基伸乙基、三亞甲基、三甲基三亞甲基、六甲基三亞甲基、四亞甲基、八甲基四亞甲基、伸丙烯基、亞乙烯基、亞環己基、1,2－伸環己烯基等。作為含矽基，可列舉亞矽烷基、二甲基亞矽烷基、二矽烯(disilene)基、四甲基二矽烯基、矽伸乙基(silaethylene) 、二甲基矽伸乙基(Dimethyl silaethylene)、四甲基矽伸乙基(tetramethyl silaethylene)等。作為含硫基，可列舉硫原子、硫伸乙基(thiaethylene)、二甲基硫伸乙基(Dimethyl thiaethylene)、硫酮基亞甲基(thioxomethylene)等。作為含氧基’可列舉氧原子、氧伸乙基(oxaethylene)、二甲基氧伸乙基(Dimethyl oxaethylene)、側氧基亞甲基(oxo methylene)等。作為含氮基可列舉亞胺基、甲基亞胺基，苯基亞胺基，氮雜伸乙基(azaethylene)，N－甲基氮雜伸乙基，N－苯基氮雜伸乙基，三甲基氮雜伸乙基，亞胺基亞甲基，N－甲基亞胺基亞甲基等。作為含鹵素基，可列舉氟亞甲基、二氟亞甲基、(三氟甲基)亞甲基、雙(三氟甲基)亞甲基、四氟伸乙基、氯亞甲基、二氯亞甲基、二溴亞甲基、二碘亞甲基等。Further, the adjacent substituents of R 1 to R 1 4 may be bonded to each other to form a ring, or may form a carbon number of 1 to 20 together with the atoms which continue to form, and may also contain an oxygen atom, a nitrogen atom or a sulfur atom. ring. Further, R 4 and R 5 may form Ra which forms a divalent substituent integrally, and R 1 2 and R 1 3 may form Rb which integrally forms a divalent substituent. Ra and Rb are a divalent substituent other than a vinyl group, preferably a hydrocarbon group having 1 to 20 carbon atoms, a mercapto group having a carbon number of 0 to 20, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, and the like. Halogen based. Examples of the above divalent hydrocarbon group include a methylene group, an exoethyl group, an ethylene group, a propyl group, an isopropylidene group, a dimethylexene group, a trimethyl-ethyl group, and a tetramethyl group. Base, trimethylene, trimethyltrimethylene, hexamethyltrimethylene, tetramethylene, octamethyltetramethylene, propylene, vinylidene, cyclohexylene, 1,2-extension Cyclohexenyl and the like. Examples of the fluorenyl group include a decylene group, a dimethyl sulfenyl group, a disilene group, a tetramethyldidecenyl group, a silaethylene group, and a dimethyl hydrazine ethyl group. Dimethyl silaethylene), tetramethyl silaethylene, and the like. Examples of the sulfur-containing group include a sulfur atom, thiaethylene, dimethyl thiaethylene, and thioxomethylene. Examples of the oxy group include an oxygen atom, an oxaethylene group, a dimethyl oxaethylene group, and an oxo methylene group. Examples of the nitrogen-containing group include an imido group, a methylimine group, a phenylimino group, an azaethylene group, an N-methyl aza extension ethyl group, and an N-phenyl aza extension ethyl group. , trimethyl aza extension ethyl, imido methylene, N-methyliminomethylene and the like. Examples of the halogen-containing group include a fluoromethylene group, a difluoromethylene group, a (trifluoromethyl)methylene group, a bis(trifluoromethyl)methylene group, a tetrafluoroextension ethyl group, and a chloromethylene group. Dichloromethylene, dibromomethylene, diiodomethylene, and the like.

作為此種鄰接之取代基形成環之茀衍生物之例，具體而言可列舉下式[Ⅱ]。Specific examples of the anthracene derivative in which the adjacent substituent forms a ring include the following formula [II].

通式[Ⅱ]中R1 5 、R1 6 、R1 7 、R1 8 、R1 9 、R2 0 、R2 1 、R2 2 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，可分別相同亦可不同。較佳係R1 5 、R1 6 、R1 7 、R1 8 、R1 9 、R2 0 、R2 1 、R2 2 為氫、碳數1~20之烴基、含碳數0~20之含矽基、含硫基、含氧基、含氮基。作為碳數1~20之烴基、含碳數0~20之含矽基、含硫基、含氧基、含氮基、含鹵素基，可例示上述之取代基。更佳為氫或碳數1~20之烴基，特佳為氫或甲基。In the general formula [II], R 1 5 , R 1 6 , R 1 7 , R 1 8 , R 1 9 , R 2 0 , R 2 1 , R 2 2 are selected from the group consisting of hydrogen, a hydrocarbon group, a thiol group, and a sulfur-containing group. The group, the oxygen-containing group, the nitrogen-containing group, and the halogen-containing group may be the same or different. Preferably, R 1 5 , R 1 6 , R 1 7 , R 1 8 , R 1 9 , R 2 0 , R 2 1 , R 2 2 are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon number of 0~ 20 containing a mercapto group, a sulfur-containing group, an oxygen-containing group, and a nitrogen-containing group. The above-mentioned substituents can be exemplified as the hydrocarbon group having 1 to 20 carbon atoms, the mercapto group having 0 to 20 carbon atoms, the sulfur-containing group, the oxygen-containing group, the nitrogen-containing group, and the halogen-containing group. More preferably, it is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, particularly preferably hydrogen or methyl.

<過渡金屬化合物><transition metal compound>

本發明之過渡金屬化合物以上述通式[Ⅲ]表示。通式[Ⅲ]中R2 3 、R2 4 、R2 5 、R2 6 、R2 7 、R2 8 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，可分別相同亦可不同，R2 3 至R2 8 之相鄰接之取代基亦可相互鍵結形成環。M為第4族過渡金屬，Y為碳原子，Q為選自鹵素、烴基、陰離子配位基或可以孤立電子配位之中性配位基之相同或不同組合，j為1~4之整數。Z為含有上述茀衍生物之亞茀基。The transition metal compound of the present invention is represented by the above formula [III]. In the general formula [III], R 2 3 , R 2 4 , R 2 5 , R 2 6 , R 2 7 , and R 2 8 are selected from the group consisting of hydrogen, a hydrocarbon group, a mercapto group, a sulfur-containing group, an oxygen-containing group, and a nitrogen-containing group. The groups and the halogen-containing groups may be the same or different, and the adjacent substituents of R 2 3 to R 2 8 may be bonded to each other to form a ring. M is a Group 4 transition metal, Y is a carbon atom, and Q is selected from the group consisting of halogen, a hydrocarbon group, an anionic ligand or the same or different combination of an ortho-coordination-neutral ligand, and j is an integer from 1 to 4. . Z is an anthracene group containing the above anthracene derivative.

作為上述烴基，可列舉甲基、乙基、正丙基、烯丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基等直鏈狀烴基；異丙基、第三丁基、戊基、3－甲基戊基、1,1－二乙基丙基、1,1－二甲基丁基、1－甲基－1－丙基丁基、1,1－丙基丁基、1,1－二甲基－2－甲基丙基、1－甲基－1－異丙基－2－甲基丙基等支鏈狀烴基；環戊基、環己基、環庚基、環辛基、降基、金剛烷基、甲基環己基、甲基金剛烷基等環狀飽和烴基；苯基、甲苯基、萘基、聯苯基、菲基、蒽基等環狀不飽和烴基；苄基，異丙苯基，1,1－二苯基乙基，三苯基甲基等環狀不飽和烴基所取代之飽和烴基等。作為含氧基可列舉甲氧基、乙氧基、苯氧基、呋喃基等。作為含氮基可列舉N－甲基胺基、N,N－二甲基胺基、N－苯基胺基、比林基(pyryl)等。作為含硫基可列舉甲硫基、噻吩基等。作為含矽基可列舉三甲基矽烷基、三乙基矽烷基、二甲基苯基矽烷基、二苯基甲基矽烷基、三苯基矽烷基等。作為含鹵素基，可列舉氟原子、三氟甲基、2,2,2－三氟乙基、氟苯基、二氟苯基、三氟苯基、五氟苯基、三氟甲基苯基、雙(三氟甲基)等含氟基，氯原子、三氯甲基、2,2,2－三氯乙基、氯苯基、二氯苯基、三氯苯基、五氯苯基、三氯甲基苯基、雙(三氯甲基)等含氯基，溴原子、溴苯基等含溴基，碘原子、碘苯基等含碘基等。Examples of the hydrocarbon group include a linear chain such as a methyl group, an ethyl group, a n-propyl group, an allyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, a n-decyl group or a n-decyl group. Hydrocarbyl; isopropyl, tert-butyl, pentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propyl a branched hydrocarbon group such as butyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl or 1-methyl-1-isopropyl-2-methylpropyl; Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, descending a cyclic saturated hydrocarbon group such as an adamantyl group, a methylcyclohexyl group or a methyladamantyl group; a cyclic unsaturated hydrocarbon group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group or a fluorenyl group; a benzyl group; A saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group such as cumyl, 1,1-diphenylethyl or triphenylmethyl. Examples of the oxygen-containing group include a methoxy group, an ethoxy group, a phenoxy group, a furyl group and the like. Examples of the nitrogen-containing group include an N-methylamino group, an N,N-dimethylamino group, an N-phenylamino group, and a pyryl group. Examples of the sulfur-containing group include a methylthio group, a thienyl group and the like. Examples of the fluorenyl group include a trimethyl decyl group, a triethyl decyl group, a dimethylphenyl decyl group, a diphenylmethyl decyl group, and a triphenyl decyl group. Examples of the halogen-containing group include a fluorine atom, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a pentafluorophenyl group, and a trifluoromethylbenzene group. Fluorinated group such as bis(trifluoromethyl) group, chlorine atom, trichloromethyl, 2,2,2-trichloroethyl, chlorophenyl, dichlorophenyl, trichlorophenyl, pentachlorobenzene a chlorine-containing group such as a trichloromethylphenyl group or a bis(trichloromethyl) group; a bromine group such as a bromine atom or a bromophenyl group; an iodine group such as an iodine atom or an iodophenyl group; and the like.

上述通式[Ⅲ]中，較佳係環戊二烯基環上取代之R2 3 、R2 4 、R2 5 、R2 6 為氫或碳數1~20之烴基。作為碳數1~20之烴基，可例示上述烴基。更佳係R2 4 、R2 6 為氫。特佳係R2 3 及/或R2 5 為碳數1~20之烴基。作為碳數1~20之烴基，可例示上述之烴基。In the above formula [III], R 2 3 , R 2 4 , R 2 5 and R 2 6 substituted on the cyclopentadienyl ring are preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is exemplified by the above hydrocarbon group. More preferably, R 2 4 and R 2 6 are hydrogen. The particularly preferred R 2 3 and/or R 2 5 is a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is exemplified by the above hydrocarbon group.

上述通式[I]中，使環戊二烯基環與茀環交聯之Y為碳原子。較佳係該Y上取代之R2 7 及R2 8 為氫、碳數1~20之烴基、碳數0~20之含矽基、含硫基、含氧基、含氮基、含鹵素基。作為碳數1~20之烴基、碳數0~20之含矽基、含硫基、含氧基、含氮基、含鹵素基，可例示上述取代基。該等可相互相同亦可不同，亦可相互鍵結形成環。作為R1 3 與R1 4 相互鍵結形成環之取代基，可列舉環亞戊基、環亞己基、環亞庚基、亞芴基、10－氫亞蒽基、二苄基亞環庚二烯基等。In the above formula [I], Y which crosslinks the cyclopentadienyl ring and the anthracene ring is a carbon atom. Preferably, the R 2 7 and R 2 8 substituted on the Y are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a mercapto group having a carbon number of 0 to 20, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, and a halogen-containing group. base. The above substituents are exemplified as the hydrocarbon group having 1 to 20 carbon atoms, the mercapto group having 0 to 20 carbon atoms, the sulfur-containing group, the oxygen-containing group, the nitrogen-containing group, and the halogen-containing group. These may be the same or different from each other, and may be bonded to each other to form a ring. Examples of the substituent in which R 1 3 and R 1 4 are bonded to each other to form a ring include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, an anthranylene group, a 10-hydroanthylene group, and a dibenzyl ring. Dienyl and the like.

上述通式[Ⅲ]中，M為第4族過渡金屬，具體而言可列舉Ti、Zr、Hf等。又，Q選自鹵素、烴基、陰離子配位基或可以孤立電子對配位之中性配位基之相同或不同之組合。j為1~4之整數，j為2以上時，Q既可相同亦可不同。作為鹵素之具體例，可列舉氟、氯、溴、碘；作為烴基之具體例，可列舉與上述相同者。作為陰離子配位基之具體例，可列舉甲氧基、第三丁氧基、苯氧基等烷氧基；醋酸酯、苯甲酸酯等羧酸酯基；甲磺酸酯、甲苯磺酸酯等磺酸酯基；二甲基醯胺基、二異丙基醯胺基、甲基苯胺基、二苯基醯胺基等醯胺基等。作為可以孤立電子對配位之中性配位基之具體例，可列舉三甲基膦、三乙基膦、三苯基膦、二苯基甲基膦等有機磷化合物，四氫呋喃、二乙醚、二烷、1,2－二甲氧基乙烷等醚類等。較佳係Q至少有1個為鹵素或烷基。In the above formula [III], M is a Group 4 transition metal, and specific examples thereof include Ti, Zr, Hf and the like. Further, Q is selected from the group consisting of halogen, a hydrocarbyl group, an anionic ligand or the same or a different combination of an ortho-electron pair-coordinating neutral ligand. j is an integer of 1 to 4, and when j is 2 or more, Q may be the same or different. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine; and specific examples of the hydrocarbon group include the same as described above. Specific examples of the anionic ligand include an alkoxy group such as a methoxy group, a third butoxy group or a phenoxy group; a carboxylate group such as an acetate or a benzoate; a mesylate or toluenesulfonic acid; a sulfonate group such as an ester; a guanamine group such as a dimethylammonium group, a diisopropylguanamine group, a methylanilino group or a diphenylguanamine group. Specific examples of the ortho-coordination-neutral ligand may include an organic phosphorus compound such as trimethylphosphine, triethylphosphine, triphenylphosphine or diphenylmethylphosphine, tetrahydrofuran or diethyl ether. two An ether such as an alkane or a 1,2-dimethoxyethane. Preferably, at least one of the groups Q is a halogen or an alkyl group.

<較佳的茀衍生物之例示><Example of a preferred anthracene derivative>

作為本發明較佳之茀衍生物，可列舉：1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀、1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀、1,3,6, 8－四甲基－1H,8H－二環戊[b,h]茀、3,6－二甲基－1H,8H－二環戊[b,h]茀、1H,8H－二環戊[b,h]茀、1,1,3－三甲基－1H－環戊[b]茀、1,3－二甲基－1H－環戊[b]茀、1,1－二甲基－1H－環戊[b]茀基茀、1－甲基－1H－環戊[b]茀、3－甲基－1H－環戊[b]茀、2,7－二甲基－1H,8H－二環戊[b,h]茀、2－甲基－1H,8H－二環戊[b,h]茀、1,1,2,3,6,7,8,8－八甲基－1H,8H－二環戊[b,h]茀、1,1,2,7,8,8－六甲基－1H,8H－二環戊[b,h]茀、3,6－二異丙基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀、3,6－二異丙基－1H,8H－二環戊[b,h]茀、3,6－二異丙基－1,3－二甲基－1H－環戊[b]茀、3－異丙基－1,1－二甲基－1H－環戊[b]茀基茀、3－異丙基－1－甲基－1H－環戊[b]茀、3,6－二異丙基－2,7－二甲基－1H,8H－二環戊[b,h]茀、3,6－二異丙基－2－甲基－1H,8H－二環戊[b,h]茀、3,6－二－第三丁基－1,1,2,7,8,8－六甲基－1H,8H－二環戊[b,h]茀、3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀、3,6－二－第三丁基－1H,8H－二環戊[b,h]茀、3,6－二－第三丁基－1,3－二甲基－1H－環戊[b]茀、3－第三丁基－1,1－二甲基－1H－環戊[b]茀基茀、3－第三丁基－1－甲基－1H－環戊[b]茀、3,6－二－第三丁基－2,7－二甲基－1H,8H－二環戊[b,h]茀、3,6－二－第三丁基－2－甲基－1H,8H－二環戊[b,h]茀、3,6－二－第三丁基－1,1,2,7,8,8－六甲基－1H,8H－二環戊[b,h]茀、1,2,9,10－四氫－二苯并[b,h]茀、1,1,10,10－四甲基－1,2,9,10－四氫－二苯并[h,h]氟、1,10－二甲基－1,2,9,10－四氫－二苯并[b,h]茀、4,7－二甲基－1,2,9,10－四氫－二苯并[b,h]茀、1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀、1H,2H－苯并[b]茀、1,1－二甲基－1H,2H－苯并[b]茀、1,1,4－三甲基－1H,2H－苯并[b]茀、1,4－二甲基－1H,2H－苯并[b]茀、4－甲基－1H,2H－苯并[b]茀、4,7－二－第三丁基－1,2,9,10－四氫－二苯并[b,h]茀、4,7－二－第三丁基－1,1,10,10－四甲基－1,2,9,10－四氫－二苯并[b,h]茀、4,7－二－第三丁基－1,10－二甲基－1,2,9,10－四氫－二苯并[b,h]茀、4－第三丁基－1,1－二甲基－1H,2H－苯并[b]茀、4－第三丁基－1－甲基－1H,2H－苯并[b]茀、3,6－二乙烯基茀、3－乙烯基茀、3,6－二－異丙烯基茀、3－異丙烯基茀、3,6－二丙烯基茀、3－丙烯基茀、3,6－二－(2－甲基異丙烯基)茀、3－(2－甲基異丙烯基)茀、3,6－二－(2－苯基異丙烯基)茀、3－(2－苯基異丙烯基)茀、3,6－二苯乙烯基茀、3－苯乙烯基氟、3,6－二－(2－苯基)丙烯基茀、3－(2－苯基)丙烯基茀、3,6－二－(1－甲基－2－苯基)丙烯基茀、3－(1－甲基－2－苯基)丙烯基茀等。其中，本發明之茀衍生物，並非受上述例示化合物任何限制者，為包含所有滿足申請專利範圍之要旨者。Preferred examples of the anthracene derivatives of the present invention include 1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorene, 1,1,8,8- Tetramethyl-1H,8H-dicyclopenta[b,h]indole, 1,3,6 , 8-tetramethyl-1H,8H-dicyclopenta[b,h]indole, 3,6-dimethyl -1H,8H-dicyclopenta[b,h]indole, 1H,8H-dicyclopenta[b,h]indole, 1,1,3-trimethyl-1H-cyclopenta[b]pyrene, 1 ,3-dimethyl-1H-cyclopenta[b]indole, 1,1-dimethyl-1H-cyclopenta[b]indolyl, 1-methyl-1H-cyclopenta[b]pyrene, 3 -methyl-1H-cyclopenta[b]indole, 2,7-dimethyl-1H,8H-dicyclopenta[b,h]indole, 2-methyl-1H,8H-dicyclopenta[b, h]茀,1,1,2,3,6,7,8,8-octamethyl-1H,8H-dicyclopenta[b,h]茀, 1,1,2,7,8,8- Hexamethyl-1H,8H-dicyclopenta[b,h]indole,3,6-diisopropyl-1,1,8,8-tetramethyl-1H,8H-dicyclopenta[b,h茀,3,6-diisopropyl-1H,8H-dicyclopenta[b,h]indole,3,6-diisopropyl-1,3-dimethyl-1H-cyclopenta[b]茀, 3-isopropyl-1,1-dimethyl-1H-cyclopenta[b]fluorenyl hydrazide, 3-isopropyl-1-methyl-1H-cyclopenta[b]pyrene, 3,6 -diisopropyl-2,7-dimethyl-1H,8H -dicyclopenta[b,h]indole, 3,6-diisopropyl-2-methyl-1H,8H-dicyclopenta[b,h]indole, 3,6-di-t-butyl- 1,1,2,7,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]indole,3,6-di-t-butyl-1,1,8,8-tetra Methyl-1H,8H-dicyclopenta[b,h]indole,3,6-di-t-butyl-1H,8H-dicyclopenta[b,h]indole,3,6-di-third Butyl-1,3-dimethyl-1H-cyclopenta[b]indole, 3-tert-butyl-1,1-dimethyl-1H-cyclopenta[b]fluorenylindole, 3-third Butyl-1-methyl-1H-cyclopenta[b]indole, 3,6-di-t-butyl-2,7-dimethyl-1H,8H-dicyclopenta[b,h]pyrene, 3,6-di-t-butyl-2-methyl-1H,8H-dicyclopenta[b,h]indole,3,6-di-t-butyl-1,1,2,7,8 ,8-hexamethyl-1H,8H-dicyclopenta[b,h]indole, 1,2,9,10-tetrahydro-dibenzo[b,h]indole, 1,1,10,10- Tetramethyl-1,2,9,10-tetrahydro-dibenzo[h,h]fluoro, 1,10-dimethyl-1,2,9,10-tetrahydro-dibenzo[b, h] 茀, 4,7-dimethyl-1,2,9,10-tetrahydro-dibenzo[b,h]indole, 1,1,4,7,10,10-hexamethyl-1 ,2,9,10-tetrahydro-dibenzo[b,h]indole, 1H,2H-benzene And [b]茀,1,1-dimethyl-1H,2H-benzo[b]indole, 1,1,4-trimethyl-1H, 2H-benzo[b]pyrene, 1,4- Dimethyl-1H,2H-benzo[b]indole, 4-methyl-1H,2H-benzo[b]indole, 4,7-di-t-butyl-1,2,9,10- Tetrahydro-dibenzo[b,h]indole, 4,7-di-t-butyl-1,1,10,10-tetramethyl-1,2,9,10-tetrahydro-dibenzo [b,h]茀,4,7-di-t-butyl-1,10-dimethyl-1,2,9,10-tetrahydro-dibenzo[b,h]茀, 4- Tributyl-1,1-dimethyl-1H,2H-benzo[b]indole, 4-t-butyl-1-methyl-1H,2H-benzo[b]indole, 3,6- Divinyl fluorene, 3-vinyl anthracene, 3,6-di-isopropenyl anthracene, 3-isopropenyl anthracene, 3,6-dipropenyl anthracene, 3-propenyl anthracene, 3,6-di- (2-Methylisopropenyl) fluorene, 3-(2-methylisopropenyl) fluorene, 3,6-di-(2-phenylisopropenyl) fluorene, 3-(2-phenylisopropene)茀, 3,6-distyryl fluorene, 3-styrylfluoro, 3,6-di-(2-phenyl)propenyl fluorene, 3-(2-phenyl)propenyl hydrazine, 3 ,6-di-(1-methyl-2-phenyl)propenyl fluorene, 3-(1 2-phenyl) fluorene-propenyl and the like. In addition, the anthracene derivatives of the present invention are not limited by the above-exemplified compounds, and all of them satisfy the gist of the scope of the patent application.

<較佳的過渡金屬化合物之例示><Example of a preferred transition metal compound>

作為本發明較佳的過渡金屬化合物，可列舉亞異丙基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3,5－二甲基環戊二烯)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對－第三丁基苯基)亞甲基(環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]氟基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三－丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[h,h]茀基)二氯化鋯、雙(對氯苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二丁基亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞環己基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苄基亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、苯基亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二苯基亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二－第三丁基－1,1,8,8－四甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯、亞異丙基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二丁基亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞環己基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苄基亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、苯基亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(甲基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(乙基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苯基亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二－對甲苯基亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氟苯基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氟苯基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氯苯基亞甲基)(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氯苯基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞異丙基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞環己基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、苯基亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞異丙基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞環己基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二－對甲苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三－丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞異丙基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞環己基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二－對甲苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氟苯基亞甲基)(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞異丙基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二丁基亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞環己基(3,5－二甲基環戊烷苯基)(3,6－二乙烯基茀基)二氯化鋯、二苄基亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、苯基亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、(苯基)(乙基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二苯基亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、二對甲苯基亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氟苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氟苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對氯苯基亞甲基)(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(間氯苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3,5－二甲基環戊二烯基)(3,6－二乙烯基茀基)二氯化鋯、亞異丙基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二丁基亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞環己基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苄基亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、苯基亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苯基亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]氟基)二氯化鋯、雙(對氟苯基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,1,0－四氫－二苯并[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯基[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－環戊二烯基)(1,1,4,7, 10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并(b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間三氟乙基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞異丙基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二丁基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞環己基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苄基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二－對甲苯基亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3－第三丁基－5－乙基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞異丙基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[h,h]茀基)二氯化鋯、二丁基亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、亞環己基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苄基亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(對甲苯基)(甲基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、(苯基)(乙基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、二對甲苯基亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間三氟甲基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氟苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氟苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對氯苯基亞甲基)(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(間氯苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯、雙(對第三丁基苯基)亞甲基(3,5－二甲基環戊二烯基)(1,1,4,7,10,10－六甲基－1,2,9,10－四氫－二苯并[b,h]茀基)二氯化鋯等。其中，本發明之過渡金屬化合物並非受上述例示化合物任何侷限，係包含所有滿足申請專利範圍之要旨者。As a preferred transition metal compound of the present invention, There may be mentioned isopropylidene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl) methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 3, 6, 8, 8-hexamethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl) methylene (3, 5-dimethylcyclopentadiene) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl) methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl) methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h]fluoro-based) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-tertiary-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopentan [h, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl) methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-di-t-butyl-1, 1, 8, 8-tetramethyl-1H, 8H-dicyclopenta [b, h] fluorenyl) zirconium dichloride, Isopropyl (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Cyclohexylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibenzylmethylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Phenylmethylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(methyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (p-tolyl) (methyl) methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(ethyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Di-p-tolylmethylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-fluorophenyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-fluorophenyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-chlorophenylmethylene) (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-chlorophenyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-tert-butylphenyl)methylene (cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Isopropyl (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibutylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Cyclohexylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibenzylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Phenylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (p-tolyl) (methyl) methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Diphenylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Isopropyl (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Cyclohexylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Phenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Isopropyl (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibutylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Cyclohexylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibenzylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Phenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-fluorophenylmethylene)(3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Isopropyl (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibutylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Cyclohexylene (3, 5-dimethylcyclopentane phenyl) (3, 6-divinylfluorenyl)zirconium dichloride, Dibenzylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Phenylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(methyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (p-tolyl) (methyl) methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, (phenyl)(ethyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Diphenylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Di-p-tolylmethylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-fluorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-chlorophenylmethylene) (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(m-chlorophenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3, 5-dimethylcyclopentadienyl) (3, 6-divinylfluorenyl)zirconium dichloride, Isopropyl (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Cyclohexylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Phenylmethylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h]fluoro-based) zirconium dichloride, Bis(p-fluorophenyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Isopropyl (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Dibutylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Cyclohexylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Dibenzylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Phenylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 1, 0-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, (p-tolyl) (methyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, (phenyl)(ethyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Diphenylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Di-p-tolylmethylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-diphenyl [b, h] fluorenyl) zirconium dichloride, Bis(m-fluorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-chlorophenylmethylene) (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(m-chlorophenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7, 10, 10-hexamethyl-1, 2, 9, 10-tetrahydro-dibenzo[b, h] fluorenyl) zirconium dichloride, Bis(p-tert-butylphenyl)methylene (3-tert-butyl-cyclopentadienyl) (1, 1, 4, 7 , 10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl) (cyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride Dibutylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10- Tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, cyclohexylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10 , 10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, dibenzylmethylene (3-tert-butyl-5- Methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl) dichloride Zirconium, phenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10- Tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1 ,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo(b,h]fluorenyl)zirconium dichloride, (p-tolyl) (methyl Methylene (3- Tributyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h] Mercapto) zirconium dichloride, (phenyl) (ethyl) methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10- Hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl ring Pentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, two p-Tolylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetra Hydrogen-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(p-trifluoromethylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) ( 1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(inter)trifluoroethyl Phenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetra Hydrogen-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(p-fluorophenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1 , 4, 7, 10, 10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(m-fluorophenyl)methylene (3-tert-butyl -5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]decyl) Zirconium dichloride, bis(p-chlorophenylmethylene) (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl- 1,2,9,10-tetrahydro-dibenzo[b,h]indenyl)zirconium dichloride, bis(m-chlorophenyl)methylene (3-tert-butyl-5-methyl ring Pentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, double (p-tert-butylphenyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2 , 9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, isopropylidene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1 ,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, dibutylmethylene (3- Tributyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h] Mercapto) zirconium dichloride Cyclohexylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-di Benzo[b,h]fluorenyl)zirconium dichloride, dibenzylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10, 10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, phenylmethylene (3-tert-butyl-5-ethyl Cyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]indenyl)zirconium dichloride, (phenyl)(methyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2, 9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, (p-tolyl)(methyl)methylene (3-tert-butyl-5-ethylcyclopentane Alkenyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, (phenyl (ethyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10 -tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4 , 7, 10, 10 - six Base-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, di-p-tolylmethylene (3-tert-butyl-5-ethyl ring Pentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, double (p-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2 , 9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(m-trifluoromethylphenyl)methylene (3-tert-butyl-5-ethyl ring Pentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, double (p-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9, 10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(m-fluorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) 1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(p-chlorophenyl) Methyl)(3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-di Benzo[b, h] mercapto) zirconium dichloride, bis(m-chlorophenyl)methylene (3-tert-butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10 - hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(p-butylphenyl)methylene (3-third Butyl-5-ethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]茀Zirconium dichloride, isopropylidene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10- Tetrahydro-dibenzo[h,h]fluorenyl)zirconium dichloride, dibutylmethylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10, 10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, cyclohexylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, dibenzylmethylene (3,5-Dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h] Mercapto) zirconium dichloride, phenylmethylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9, 10-tetrahydro-dibenzo[b,h]fluorenyl)dichloro Zirconium, (phenyl)(methyl)methylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9, 10-tetrahydro-dibenzo[b,h]indenyl)zirconium dichloride, (p-tolyl)(methyl)methylene (3,5-dimethylcyclopentadienyl) (1, 1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, (phenyl)(ethyl) Methyl (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b, h] mercapto) zirconium dichloride, diphenylmethylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2 , 9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, di-p-tolylmethylene (3,5-dimethylcyclopentadienyl) (1,1, 4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(p-trifluoromethylphenyl) Methyl (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b, h] mercapto) zirconium dichloride, bis(m-trifluoromethylphenyl)methylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10- Hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]茀Zirconium dichloride, bis(p-fluorophenyl)methylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1, 2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(m-fluorophenyl)methylene (3,5-dimethylcyclopentadienyl) 1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, bis(p-chlorophenyl) Methyl) (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b , h] mercapto) zirconium dichloride, bis(m-chlorophenyl)methylene (3,5-dimethylcyclopentadienyl) (1,1,4,7,10,10-hexa 1,2-, 9,10,10-tetrahydro-dibenzo[b,h]indenyl)zirconium dichloride, bis(p-butylphenyl)methylene (3,5-dimethyl Cyclopentadienyl) (1,1,4,7,10,10-hexamethyl-1,2,9,10-tetrahydro-dibenzo[b,h]fluorenyl)zirconium dichloride, etc. . Wherein, the transition metal compound of the present invention is not limited by the above-exemplified compounds, and all of the items satisfying the scope of the patent application are included.

本發明中，將骨架中具有通式[I]所表示之茀衍生物之3位及/或6位取代基之碳－碳雙鍵，以公知之方法，進一步施加化學變化之衍生物，例如以過酸等將碳－碳雙鍵環氧化之衍生物，以含活性氫之化合物將該環氧衍生物進行開環之衍生物等，在可表現本發明之聚合活性之前提下，則可不受限制地使用。In the present invention, a carbon-carbon double bond having a 3-position and/or a 6-position substituent of the anthracene derivative represented by the general formula [I] in the skeleton is further subjected to a chemically-changed derivative by a known method, for example, a derivative obtained by epoxidizing a carbon-carbon double bond with a peracid or the like, a derivative obtained by ring-opening the epoxy derivative with an active hydrogen-containing compound, or the like, which can be removed before the polymerization activity of the present invention can be expressed, or not Restricted use.

<茀衍生物的製造方法><Method for producing anthracene derivative>

本發明之茀衍生物可以公知之方法進行製造，製造法並無特別之限制。作為公知之方法，例如可列舉本申請人之WO01/27124號公報。首先，通式[I]之前驅體化合物(1)可以通式[A]之方法進行製造。The anthracene derivative of the present invention can be produced by a known method, and the production method is not particularly limited. As a known method, for example, WO01/27124 of the present applicant is mentioned. First, the precursor compound (1) of the general formula [I] can be produced by the method of the general formula [A].

式中，R1 ~R1 4 係與通式[I]相同。X1 、X2 可分別相同亦可不同，可列舉鹵素原子、三氟甲基磺酸基、磺酸基等。藉由以公知之方法使式(1)之化合物偶合，獲得通式[I]之化合物。該偶合反應，係例如使用一種或2種以上選自除了銅、鎂、鋅、鋰、鈉、鉀等金屬，或烷基鋰、鹵化烷基鎂、鹵化芳基鎂等有機金屬化合物等之外，於氯化鎳、硝酸鎳等鎳鹽或氯化鈀、乙酸鈀等鈀鹽中根據需要添加配位基所得之過渡金屬觸媒等，於無溶劑或有機溶劑中，以－80℃~300℃範圍之條件下進行。In the formula, R 1 to R 1 4 are the same as the general formula [I]. X 1 and X 2 may be the same or different, and examples thereof include a halogen atom, a trifluoromethylsulfonate group, and a sulfonic acid group. The compound of the formula [I] is obtained by coupling a compound of the formula (1) in a known manner. The coupling reaction is, for example, one or two or more selected from the group consisting of metals other than copper, magnesium, zinc, lithium, sodium, potassium, or an organic metal compound such as an alkyl lithium, an alkyl magnesium halide, or an aryl magnesium halide. a transition metal catalyst obtained by adding a ligand to a nickel salt such as nickel chloride or nickel nitrate or a palladium salt such as palladium chloride or palladium acetate, or the like, in a solvent-free or organic solvent, at -80 ° C to 300 Performed under the conditions of °C.

又，通式[Ⅱ]之化合物可以如通式[B]之方法進行製造。Further, the compound of the general formula [II] can be produced by the method of the general formula [B].

式中，R1 5 ~R2 2 係與通式[Ⅱ]相同。屬於中間體之以式(2)表示之化合物，係將茀與公知之α,β－不飽和酮作為原料，於無溶劑或有機溶劑中，於－100℃~200℃下，根據需要於觸媒之存在下進行。成為原料之α,β－不飽和酮並無特別之限制，例如可列舉丁－3－烯－2－酮、戊－3－烯－2－酮、4－甲基－戊－3－烯－2－酮、4－苯基－丁－3－烯－2－酮、1－苯基丙烯酮、1,3－二苯基丙烯酮、2－甲基丙烯酮、2,4－二甲基－戊－3－烯－2－酮、4,4－二甲基－戊－1－烯－3－酮、2,2－二甲基－己－4－烯－3－酮、2,2,5－三甲基－己－4－烯－3－酮等。該等相對於茀可使用1~20當量，較佳1.8~10當量，更佳2~5當量。溶劑無特別之限制，可於無溶劑或二氯甲烷、氯仿、四氯化碳、氯苯、二氯苯、硝基苯、硝基甲烷、二硫化碳、己烷、庚烷、癸烷、環己烷等溶劑中進行。該反應可根據需要添加觸媒。作為觸媒，可使用1種或2種以上之鹽酸、氯化氫、硫酸、硝酸、磷酸、聚磷酸、五氧化二磷、三氟甲基磺酸、甲基磺酸、氫氟酸、氯化鋁、氯化錫、氯化鐵、氯化鋅、氟化硼、氯化銅、氯化水銀、四氯化鈦、四氯化鋯、四氯化鉿、溴化鋁、溴化鉄、氯化鈹、鋅、氯化鎵、或雜多酸、氧化鋁、沸石等固體酸等之公知之路易斯酸。In the formula, R 1 5 to R 2 2 are the same as those of the general formula [II]. A compound represented by the formula (2) which is an intermediate, which is obtained by using ruthenium and a known α,β-unsaturated ketone as a raw material in a solvent-free or organic solvent at -100 ° C to 200 ° C, as needed Conducted in the presence of the media. The α,β-unsaturated ketone to be a raw material is not particularly limited, and examples thereof include but-3-en-2-one, pent-3-en-2-one, and 4-methyl-pent-3-ene. 2-keto, 4-phenyl-but-3-en-2-one, 1-phenylpropenone, 1,3-diphenylpropenone, 2-methylpropenone, 2,4-dimethyl -pent-3-en-2-one, 4,4-dimethyl-pent-1-en-3-one, 2,2-dimethyl-hex-4-en-3-one, 2,2 , 5-trimethyl-hex-4-en-3-one, and the like. These may be used in an amount of from 1 to 20 equivalents, preferably from 1.8 to 10 equivalents, more preferably from 2 to 5 equivalents, per mole. The solvent is not particularly limited and may be in the absence of a solvent or dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, nitrobenzene, nitromethane, carbon disulfide, hexane, heptane, decane, cyclohexane. It is carried out in a solvent such as an alkane. This reaction can add a catalyst as needed. As the catalyst, one or more kinds of hydrochloric acid, hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, trifluoromethanesulfonic acid, methanesulfonic acid, hydrofluoric acid, and aluminum chloride can be used. , tin chloride, ferric chloride, zinc chloride, boron fluoride, copper chloride, silver chloride, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, aluminum bromide, antimony bromide, chlorination A well-known Lewis acid such as cerium, zinc, gallium chloride, or a solid acid such as a heteropoly acid, an alumina or a zeolite.

自式(2)所表示之中間體合成通式[Ⅱ]所表示之茀衍生物係可依與上述式(2)所表示之中間體之合成相同之方式進行。再者，中間體(2)可分離，亦可不分離而直接導入至通式[Ⅱ]所示之茀衍生物中。The intermediate derivative represented by the formula (II) can be synthesized in the same manner as the synthesis of the intermediate represented by the above formula (2). Further, the intermediate (2) may be isolated or directly introduced into the anthracene derivative represented by the general formula [II] without isolation.

<過渡金屬化合物的製造方法><Method for Producing Transition Metal Compound>

本發明之過渡金屬化合物可以公知之方法進行製造，製造法並無特別之限制。作為公知之製造方法，例如可列舉本申請人之WO01/27124號公報。例如，通式[Ⅲ]之化合物可依如下之步驟進行製造。首先通式[Ⅲ]之前驅體化合物(9)可以通式[C]或[D]之方法進行製造。The transition metal compound of the present invention can be produced by a known method, and the production method is not particularly limited. As a known manufacturing method, for example, WO01/27124 of the present applicant is mentioned. For example, the compound of the general formula [III] can be produced by the following procedure. First, the precursor compound (9) of the general formula [III] can be produced by the method of the general formula [C] or [D].

式中，R3 ~R2 6 、Y係與通式[I]相同，L為鹼金屬。G1 、G2 為鹵素或陰離子配位基，該等可相同，或者亦可為不同之組合。又，可認為(1)、(2)、(5)係存在僅於環戊二烯基環上之雙鍵位置不同之異構體，雖僅例示該等中之一種，但亦可為環戊二烯基環中僅雙鍵位置不同之其他異構體，或亦可為該等之混合物。In the formula, R 3 to R 2 6 and Y are the same as the general formula [I], and L is an alkali metal. G 1 and G 2 are halogen or an anionic ligand, and these may be the same or may be different combinations. Further, it is considered that (1), (2), and (5) are isomers having different positions of the double bond only on the cyclopentadienyl ring, and although only one of them is exemplified, it may be a ring. Other isomers having only different positions of the double bond in the pentadienyl ring, or a mixture thereof.

作為上述通式[C]、[D]反應中所使用之鹼金屬，可列舉鋰、鈉或鉀，作為鹼土類金屬可列舉鎂、鈣。又，作為鹵素，可列舉氟、氯、溴、碘。作為陰離子配位基之具體例，可列舉甲氧基、第三丁氧基、苯氧基等烷氧基；醋酸酯、苯甲酸酯等羧酸酯基；甲磺酸酯、甲苯磺酸酯等磺酸酯基等。Examples of the alkali metal used in the reaction of the above general formulas [C] and [D] include lithium, sodium or potassium, and examples of the alkaline earth metal include magnesium and calcium. Further, examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the anionic ligand include an alkoxy group such as a methoxy group, a third butoxy group or a phenoxy group; a carboxylate group such as an acetate or a benzoate; a mesylate or toluenesulfonic acid; a sulfonate group such as an ester.

繼而，以下表示自通式(9)之前驅體化合物製造過渡金屬化合物之例，但其並非為限制發明範圍者，亦可以公知之任一方法進行製造。以通式[C]、[D]之反應所得之通式(9)之前驅體化合物，係於有機溶劑中於反應溫度為－80℃~200℃之範圍與鹼金屬、氫化驗金屬或有機鹼金屬相接觸，而作成二鹼金屬鹽。作為上述反應中所使用之有機溶劑，可列舉戊烷、己烷、庚烷、環己烷、癸烷等脂肪族烴；或苯、甲苯、二甲苯等芳香族烴；或四氫呋喃、二乙基醚、二烷、1,2－二甲氧基乙烷、第三丁基甲基醚、環戊基甲基醚等醚；或二氯甲烷、氯仿等鹵化烴等。又，作為上述反應中所使用之鹼金屬，可列舉鋰、鈉、鉀等；作為氫化驗金屬，可列舉氫化鈉、氫化鉀等；作為有機鹼金屬可列舉甲基鋰、丁基鋰、苯基鋰等。Next, an example in which a transition metal compound is produced from a precursor compound of the general formula (9) is shown below, but it is not intended to limit the scope of the invention, and it may be produced by any known method. The precursor compound of the formula (9) obtained by the reaction of the general formulas [C] and [D] is in an organic solvent at a reaction temperature of -80 ° C to 200 ° C in the range of alkali metal, hydrogenation metal or organic The alkali metal phase is contacted to form an alkali metal salt. Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decane; or aromatic hydrocarbons such as benzene, toluene, and xylene; or tetrahydrofuran or diethyl. Ether, two An ether such as an alkane, 1,2-dimethoxyethane, a third butyl methyl ether or a cyclopentyl methyl ether; or a halogenated hydrocarbon such as dichloromethane or chloroform. Further, examples of the alkali metal used in the above reaction include lithium, sodium, and potassium; and examples of the hydrogenation metal include sodium hydride and potassium hydride; and examples of the organic alkali metal include methyl lithium, butyl lithium, and benzene. Lithium and so on.

繼而可使上述所得之二鹼金屬鹽，與以通式(13)MJk………(13)(式中，M為選自週期表第4族之金屬，J為選自鹵素、陰離子配位基或可以孤立電子對配位之中性配位基之相同或不同之組合，k為3~6之整數。)所表示之化合物於有機溶煤中進行反應，合成通式[Ⅲ]表示之二茂金屬化合物。作為通式(13)所表示之化合物的較佳具體例，可列舉三價或四價鈦氟化物、氯化物、溴化物以及碘化物，四價鋯氟化物、氯化物、溴化物以及碘化物，四價鉿氟化物、氯化物、溴化物以及碘化物，或該等之四氫呋喃、二乙基醚、二烷或與1,2－二甲氧基乙烷等醚類之錯合物。又，作為可使用之有機溶劑可列舉與上述相同者。上述所得之二鹼金屬鹽與通式(13)所表示之化合物的反應，較佳係可依等莫耳反應進行，於上述有機溶劑中，於反應溫度為－80℃~200℃之範圍進行。反應所得之二茂金屬化合物可藉萃取、再結晶、昇華等方法，進行分離．精製。以如此之方法所得之本發明之過渡金屬化合物係以質子核磁共振光譜、1 3 C核磁共振光譜、質量分析、以及元素分析等分析方法進行鑒定。Then, the dibasic metal salt obtained above can be combined with the formula (13) MJk (...) (wherein M is a metal selected from Group 4 of the periodic table, and J is selected from a halogen, an anion coordination The group may be the same or a different combination of the ortho-neutral pair-neutral neutral ligands, k is an integer from 3 to 6. The compound represented by the reaction is reacted in an organic dissolved coal to synthesize the formula [III] A metallocene compound. Preferred examples of the compound represented by the formula (13) include trivalent or tetravalent titanium fluorides, chlorides, bromides, and iodides, tetravalent zirconium fluorides, chlorides, bromides, and iodides. , tetravalent europium fluoride, chloride, bromide and iodide, or such tetrahydrofuran, diethyl ether, two An alkane or a complex with an ether such as 1,2-dimethoxyethane. Further, examples of the organic solvent that can be used include the same as described above. The reaction of the above-mentioned dibasic metal salt with the compound represented by the formula (13) is preferably carried out according to the molar reaction, and the reaction temperature is in the range of from -80 ° C to 200 ° C in the above organic solvent. . The dimetallocene compound obtained by the reaction can be separated by extraction, recrystallization, sublimation and the like. refined. The transition metal compound of the present invention obtained in such a manner is identified by proton nuclear magnetic resonance spectroscopy, 1 3 C nuclear magnetic resonance spectroscopy, mass analysis, and elemental analysis.

<將過渡金屬供給於烯烴聚合用觸媒時之較佳形態><Preferred form when a transition metal is supplied to a catalyst for olefin polymerization>

繼而對使用本發明之過渡金屬化合物作為烯烴聚合觸媒之情形時之較佳形態進行說明。於使用本發明之過渡金屬化合物作為烯烴聚合用觸媒之情形時，較佳係觸媒成分含有：(A)上述過渡金屬化合物；(B)選自與(B－1)有機金屬化合物、(B－2)有機鋁氧化物化合物、以及(B－3)與過渡金屬化合物(A)反應而形成離子對之化合物之至少一種化合物；進而根據需要含有(C)粒子狀載體。Next, a preferred embodiment in the case of using the transition metal compound of the present invention as an olefin polymerization catalyst will be described. In the case where the transition metal compound of the present invention is used as a catalyst for olefin polymerization, it is preferred that the catalyst component contains: (A) the above transition metal compound; (B) is selected from (B-1) an organometallic compound, ( B-2) an organoaluminum oxide compound and (B-3) at least one compound which reacts with the transition metal compound (A) to form an ion pair; and further contains (C) a particulate carrier as needed.

以下，對各成分加以具體說明。Hereinafter, each component will be specifically described.

<(B－1)有機金屬化合物><(B-1) organometallic compound>

作為本發明所使用之有機金屬化合物(B－1)，具體而言係使用下述第1、2族以及第12、13族之有機金屬化合物。As the organometallic compound (B-1) used in the present invention, specifically, the following organometallic compounds of Groups 1, 2 and 12 and 13 are used.

(B－1a)通式：Ra mAl(ORb )nHpEq(式中，Ra以及Rb相互可相同亦可不同，表示碳數為1~15、較佳1~4之烴基，E表示鹵素原子，m為0<m≦3、n為0≦n<3、p為0≦p<3、q為0≦q<3之數，且m＋n＋p＋q＝3)所表示之有機鋁化合物。作為此種化合物之具體例，可列舉三甲基鋁、三乙基鋁、三異丁基鋁、二異丁基氫化鋁等。(B-1a) Formula: R a mAl(OR b )nHpEq (wherein, Ra and Rb may be the same or different from each other, and represent a hydrocarbon group having a carbon number of 1 to 15, preferably 1 to 4, and E represents a halogen atom. m is an organoaluminum compound represented by 0 < m ≦ 3, n is 0 ≦ n < 3, p is 0 ≦ p < 3, q is 0 ≦ q < 3, and m + n + p + q = 3). Specific examples of such a compound include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and diisobutyl aluminum hydride.

(B－1b)通式：M2 A1Ra 4 (式中，M2 表示Li、Na或K，Ra 表示碳數為1~15、較佳1~4之烴基)所表示之第1族金屬與鋁之錯合烷基化物。作為此種化合物，可例示LiAl(C2 H5 )5 、LiAl(C7 H1 5 )4 等。(B-1b) Formula: M 2 A1R a 4 (wherein M 2 represents Li, Na or K, and R a represents a hydrocarbon group having a carbon number of 1 to 15, preferably 1 to 4) A mis-alkylate of metal to aluminum. As such a compound, LiAl(C 2 H 5 ) 5 , LiAl(C 7 H 1 5 ) 4 or the like can be exemplified.

(B－1c)通式：Ra Rb M3 (式中，Ra 以及Rb 相互可相同亦可不同，表示碳數為1~15、較佳1~4之烴基，M3 為Mg、Zn或Cd)所表示之第2族或第12族金屬之二烷基化合物。上述有機金屬化合物(B－1)中，較佳為有機鋁化合物。又，此種有機金屬化合物(B－1)可單獨使用亦可將2種以上組合使用。(B-1c) Formula: R a R b M 3 (wherein R a and R b may be the same or different from each other, and represent a hydrocarbon group having a carbon number of 1 to 15, preferably 1 to 4, and M 3 is Mg. a dialkyl compound of a Group 2 or Group 12 metal represented by Zn or Cd). Among the above organometallic compounds (B-1), an organoaluminum compound is preferred. Further, the organometallic compound (B-1) may be used alone or in combination of two or more.

<(B－2)有機鋁氧化物化合物><(B-2) organoaluminum oxide compound>

於本發明中使用之有機鋁氧化物化合物(B－2)，可為習知公知之鋁氧烷，又，亦可為日本專利持開平2－78687號公報中例示之苯不溶性有機鋁氧化物化合物。The organoaluminum oxide compound (B-2) used in the present invention may be a well-known aluminoxane, or may be a benzene-insoluble organoaluminum oxide exemplified in Japanese Patent Laid-Open No. Hei 2-78687. Compound.

習知公知之鋁氧烷係例如可以下述之方法進行製造，通常為獲得碳氫化合物溶劑之溶液。The aluminoxane which is known in the art can be produced, for example, by the following method, usually a solution obtained by obtaining a hydrocarbon solvent.

(1)於含吸著水之化合物或含結晶水之鹽類，例如氯化鎂水合物、硫酸銅水合物、硫酸鋁水合物、硫酸鎳水合物、氯化亞鈰水合物等碳氫化合物媒介懸濁液中，添加三烷基鋁等有機鋁化合物，使吸著水或結晶水與有機鋁化合物反應之方法。(1) Hydrocarbon medium suspensions of compounds containing sorbed water or salts containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and hydrazine chloride hydrate In the turbid liquid, an organoaluminum compound such as trialkylaluminum is added to react the sorbed water or the crystallization water with the organoaluminum compound.

(2)於苯、甲苯、二乙基醚、四氫呋喃等媒介中，使水、冰或水蒸氣直接作用於三烷基鋁等之有機鋁化合物上之方法。(2) A method in which water, ice or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

(3)於癸烷、苯、甲苯等媒介中使三烷基鋁等有機鋁化合物，與氧化二甲基錫、氧化二丁基錫等之有機錫氧化物反應之方法。(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

再者，上述鋁氧烷亦可含有少量有機金屬成分。又，可自回收之上述鋁氧烷溶液中蒸餾去除溶劑或未反應之有機鋁化合物後，使其再溶解於溶劑中或者懸濁於鋁氧烷之貧溶劑中。作為製備鋁氧烷時所使用之有機鋁化合物，具體而言可列舉與例示為屬於上述(B－1a)之有機鋁化合物者相同之有機鋁化合物。該等中，較佳為三烷基鋁、三環烷基鋁，特佳為三甲基鋁。上述之有機鋁化合物可單獨使用1種或將2種組合使用。Further, the aluminoxane may contain a small amount of an organic metal component. Further, the solvent or the unreacted organoaluminum compound may be distilled off from the recovered aluminoxane solution, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane. Specific examples of the organoaluminum compound used in the preparation of the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound of the above (B-1a). Among these, a trialkyl aluminum or a tricycloalkyl aluminum is preferable, and trimethyl aluminum is particularly preferable. The above organoaluminum compounds may be used singly or in combination of two or more.

又，本發明中所使用之苯基不溶性之有機鋁氧化物化合物係溶解於60℃苯中之Al成分以Al原子予以換算，通常為10%以下，較佳5%以下，特佳2%以下者，即，較佳係對於苯而言屬不溶性或難溶性者。該等之有機鋁氧化物化合物(B－2)可單獨使用1種或將2種以上組合使用。Further, the phenyl-insoluble organoaluminum oxide compound used in the present invention is an Al component dissolved in benzene at 60 ° C in terms of Al atom, and is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less. Preferably, those which are insoluble or poorly soluble for benzene. These organoaluminum oxide compounds (B-2) may be used alone or in combination of two or more.

<(B－3)與過渡金屬化合物反應而形成離子對之化合物><(B-3) reacts with a transition metal compound to form an ion pair compound>

作為與本發明中所使用之過渡金屬化合物(A)反應而形成離子對之化合物(B－3)(以下，稱為「離子化離子性化合物」)可列舉日本專利特開平1－501950號公報、日本專利特開平1－502036號公報、日本專利特開平3－179005號公報、日本專利特開平3－179006號公報、日本專利特開平3－207703號公報、日本專利特開平3－207704號公報、USP－5321106號等中所揭示之路易斯酸、離子性化合物、硼烷化合物以及碳硼烷化合物等。進而，亦可列舉雜多化合物以及異多化合物。此種離子化離子性化合物(B－3)可單獨使用或將2種以上組合使用。使用本發明之過渡金屬化合物作為烯烴聚合用觸媒之情形時，若併用作為助觸媒成分之甲基鋁氧烷等有機鋁氧化物化合物(B－2)，則對烯烴化合物表現出特別高之聚合活性。The compound (B-3) (hereinafter referred to as "ionized ionic compound") which forms an ion pair by reacting with the transition metal compound (A) used in the present invention is exemplified by Japanese Patent Laid-Open No. Hei 1-501950 Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. A Lewis acid, an ionic compound, a borane compound, a carborane compound, or the like disclosed in USP-5321106 or the like. Further, a heteropoly compound and a heteropoly compound may also be mentioned. Such an ionizing ionic compound (B-3) may be used alone or in combination of two or more. When the transition metal compound of the present invention is used as a catalyst for olefin polymerization, when an organoaluminum oxide compound (B-2) such as methylaluminoxane as a catalyst component is used in combination, the olefin compound is particularly high. Polymerization activity.

又，本發明相關之烯烴聚合用觸媒可使用上述過渡金屬化合物(A)、選自有機金屬化合物(B－1)、有機鋁氧化物化合物(B－2)、以及離子化離子性化合物(B－3)之至少1種之化合物(B)，同時亦可根據需要使用載體(C)。Further, the catalyst for olefin polymerization according to the present invention may be a transition metal compound (A) selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxide compound (B-2), and an ionized ionic compound ( At least one of the compounds (B) of B-3), and the carrier (C) may be used as needed.

<(C)載體><(C) carrier>

於本發明中使用之載體(C)為無機或有機化合物，為顆粒狀至微粒子狀之固體。作為無機化合物，較佳的為多孔質氧化物、無機氯化物、黏土、黏土礦物或離子交換性層狀化合物。The carrier (C) used in the present invention is an inorganic or organic compound and is a particulate to microparticle-like solid. As the inorganic compound, a porous oxide, an inorganic chloride, a clay, a clay mineral or an ion-exchange layered compound is preferred.

作為多孔質氧化物，具體而言係使用SiO2 、Al2 O3 、MgO、ZrO2 、TiO2 、B2 O3 、CaO、ZnO、BaO、ThO2 等，或含有該等之複合物或混合物，例如可使用天然或合成沸石、SiO2 －MgO、SiO2 －Al2 O3 、SiO2 －TiO2 、SiO2 －V2 O5 、SiO2 －Cr2 O3 、SiO2 －TiO2 －MgO等。該等中，較佳為以SiO2 及/或Al2 O3 為主成分者。此種多孔質氧化物因種類以及製法而其性狀不同，但本發明中適合使用之載體係粒徑為5~300 μ m，更佳10~100 μ m，比表面積為50~1000 m2 /g，更佳200~900 m2 /g之範圍，細孔容積為0.3~3.0 cm3 /g之範圍。此種載體根據需要於100~1000℃，較佳於150~700℃下進行燒成而使用。Specific examples of the porous oxide include SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , or the like, or a composite thereof or As the mixture, for example, natural or synthetic zeolite, SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , SiO 2 -TiO 2 can be used. -MgO, etc. Among these, it is preferable to use SiO 2 and/or Al 2 O 3 as a main component. Such a porous oxide has different properties depending on the type and the production method, but the carrier suitable for use in the present invention has a particle diameter of 5 to 300 μm, more preferably 10 to 100 μm, and a specific surface area of 50 to 1000 m 2 / g, more preferably in the range of 200 to 900 m 2 /g, and the pore volume is in the range of 0.3 to 3.0 cm 3 /g. Such a carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, as needed.

作為無機氯化物可使用MgCl2 、MgBr2 、MnCl2 、MnBr2 等。無機氯化物可直接使用，亦可使用球磨機、振動磨碎機予以粉碎後使用。又，將無機氯化物溶解於醇等溶劑中之後，亦可使用藉由析出劑使之析出為微粒子狀者。As the inorganic chloride, MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 or the like can be used. The inorganic chloride can be used as it is, or it can be pulverized by using a ball mill or a vibration mill. Further, after the inorganic chloride is dissolved in a solvent such as an alcohol, it may be precipitated into a fine particle by a precipitating agent.

於本發明中使用之黏土係通常以黏土礦物作為主成分而構成。又，於本發明中使用之離子交換性層狀化合物為具有經由離子鍵所構成之面以相互較弱之鍵結力平行堆積之結晶結構的化合物，係可交換所含有之離子者。大部分黏土礦物為離子交換性層狀化合物。又，作為該等之黏土、黏土礦物、離子交換性層狀化合物，不限於天然產者，亦可使用人工合成物。又，作為黏土、黏土礦物或離子交換性層狀化合物，可例示黏土、黏土礦物、又、具有六方最密堆積型、銻型、CdCl2 型、CdI2 型等層狀結晶構造之離子結晶性化合物等。作為此種黏土、黏土礦物、可列舉高嶺土、膨潤土、木節土、蛙目黏土、鋁英石、矽鐵土、葉蠟石、雲母群、蒙脫石群、蛭石、綠泥石群、坡縷石、高嶺石、珍珠石、狄克石、多水高嶺土等，作為離子交換性層狀化合物，可列舉α－Zr(HAsO4 )2 ．H2 O、α－Zr(HPO4 )2 、α－Zr(KPO4 )2 ．3H2 O、α－Ti(HPO4 )2 、α－Ti(HAsO4 )2 ．H2 O、α－Sn(HPO4 )2 ．H2 O、γ－Zr(HPO4 )2 、γ－Ti(HPO4 )2 、γ－Ti(NH4 PO4 )2 ．H2 O等多價金屬之結晶性酸性鹽等。最好對於本發明中使用之黏土、黏土礦物實施化學處理。作為化學處理，可使用去除附著於表面之雜質之表面處理、對黏土結晶結構造成影響之處理等任意者。作為化學處理，具體而言可列舉酸處理、鹼處理、鹽類處理、有機物處理等。The clay system used in the present invention is usually composed of a clay mineral as a main component. Further, the ion-exchange layered compound used in the present invention is a compound having a crystal structure in which the surface formed by the ionic bond is deposited in parallel with each other with a weak bonding force, and the ion contained therein can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as such clays, clay minerals, and ion-exchange layered compounds, artificial synthetics may be used without being limited to natural producers. Further, as the clay, the clay mineral, or the ion-exchange layered compound, ionic crystallinity of a layered crystal structure such as a clay, a clay mineral, or a hexagonal closest packing type, a 锑 type, a CdCl 2 type, or a CdI 2 type can be exemplified. Compounds, etc. As such clays and clay minerals, kaolin, bentonite, woody soil, frog clay, aluminite, samarium, pyrophyllite, mica group, montmorillonite group, vermiculite, chlorite group, Examples of the ion-exchange layered compound include palygorskite, kaolinite, perlite, dickite, and kaolinite, and α-Zr(HAsO 4 ) 2 . H 2 O, α-Zr(HPO 4 ) 2 , α-Zr(KPO 4 ) 2 . 3H 2 O, α-Ti(HPO 4 ) 2 , α-Ti(HAsO 4 ) 2 . H 2 O, α-Sn(HPO 4 ) 2 . H 2 O, γ-Zr(HPO 4 ) 2 , γ-Ti(HPO 4 ) 2 , γ-Ti(NH 4 PO 4 ) 2 . A crystalline acid salt of a polyvalent metal such as H 2 O or the like. It is preferable to carry out chemical treatment on the clay and clay mineral used in the present invention. As the chemical treatment, any treatment such as surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure of the clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

於本發明中使用之離子交換性層狀化合物，亦可為藉由利用離子交換性，將層間交換性離子與其他大體積離子進行交換，而擴大層間狀態之層狀化合物。此種大體積離子係擔負支持層狀構造之功效，通常稱之為柱(pillar)。又，將於此種層狀化合物之層間導入其他物質者稱之為嵌入(intercalation)。作為嵌入之客體化合物，可列舉TiCl4 、ZrCl4 等陽離子性無機化合物；Ti(OR)4 、Zr(OR)4 、PO(OR)3 、B(OR)3 等烷氧基金屬(R為烴基等)；[Al1 3 O4 (OH)2 4 ]7 ＋ 、[Zr4 (OH)1 4 ]2 ＋ 、[Fe3 O(OCOCH3 )6 ]＋ 等金屬氫氧化物離子等。該等化合物可單獨使用亦可將2種以上組合使用。又，嵌入該等化合物時，亦可使將Si(OR)4 、Al(OR)3 、Ge(OR)4 等烷氧基金屬(R為烴基等)等加水分解所獲得之聚合物、SiO2 等膠體狀無機化合物共存。又，作為柱，可列舉藉由將上述金屬氫氧化物離子嵌入層間後進行加熱脫水所生成之氧化物等。該等中，較佳者為黏土或黏土礦物，特佳為蒙脫石、蛭石、針鈉鈣石、鋰鎂雲母以及合成雲母。The ion-exchange layered compound used in the present invention may be a layered compound in which an interlayer exchangeable ion is exchanged with other large-volume ions by ion exchange property to expand an interlayer state. Such bulky ions are responsible for supporting the layered structure and are commonly referred to as pillars. Further, introduction of other substances between the layers of such a layered compound is referred to as intercalation. Examples of the guest compound to be embedded include a cationic inorganic compound such as TiCl 4 or ZrCl 4 ; an alkoxy metal such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 or B(OR) 3 (R is a hydrocarbon group or the like; a metal hydroxide ion such as [Al 1 3 O 4 (OH) 2 4 ] 7 + , [Zr 4 (OH) 1 4 ] 2 + , [Fe 3 O(OCOCH 3 ) 6 ] + or the like. These compounds may be used alone or in combination of two or more. Further, when these compounds are embedded, a polymer obtained by hydrolyzing an alkoxide metal such as Si(OR) 4 , Al(OR) 3 or Ge(OR) 4 (R is a hydrocarbon group) or the like, or SiO may be used. 2 colloidal inorganic compounds coexist. Further, examples of the column include an oxide formed by incorporation of the above metal hydroxide ions between layers, followed by heating and dehydration. Among these, clay or clay minerals are preferred, and montmorillonite, vermiculite, acupuncture, lithium magnesium mica, and synthetic mica are particularly preferred.

作為有機化合物，可列舉粒徑為5~300 μ m範圍中之顆粒狀至微粒子狀固體。具體而言，可例示以乙烯、丙烯、1－丁烯、4－甲基－1－戊烯等碳數為2~14之α－烯烴作為主成分所生成之(共)聚合體，以乙烯環己烷、苯乙烯作為主成分所生成之(共)聚合體，以及該等之變形體。Examples of the organic compound include particulate to microparticle-like solids having a particle diameter of 5 to 300 μm. Specifically, a (co)polymer produced by using an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene as a main component, and ethylene can be exemplified. (co)polymers formed by using cyclohexane and styrene as main components, and the deformed bodies thereof.

本發明相關之烯烴聚合用觸媒係含有本發明之過渡金屬化合物(A)、選自有機金屬化合物(B－1)、有機鋁氧化物化合物(B－2)、以及離子化離子性化合物(B－3)中之至少1種之化合物(B)，根據需要再含有載體(C)，同時亦根據需要可含有下述之特定有機化合物成分(D)。The catalyst for olefin polymerization according to the present invention contains the transition metal compound (A) of the present invention, an organometallic compound (B-1), an organoaluminum oxide compound (B-2), and an ionized ionic compound ( The compound (B) of at least one of B-3) may further contain a carrier (C) as needed, and may further contain the following specific organic compound component (D) as needed.

<(D)有機化合物成分><(D) Organic Compound Composition>

本發明中，有機化合物成分(D)可根據需要，以提高聚合性能以及生成聚合物之物性為目的而使用。作為此種有機化合物，可列舉醇類、苯酚性化合物、羧酸、磷化合物以及磺酸鹽等，但並非侷限於此。In the present invention, the organic compound component (D) can be used for the purpose of improving the polymerization performance and the physical properties of the polymer, as needed. Examples of such an organic compound include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates, but are not limited thereto.

聚合時，可任意選擇各成分之使用法、添加順序，可例示如下之方法。In the case of polymerization, the method of use and the order of addition of each component can be arbitrarily selected, and the following methods can be exemplified.

(1)將成分(A)單獨加入至聚合器中之方法。(1) A method of separately adding the component (A) to a polymerization vessel.

(2)將成分(A)以及成分(B)以任意順序加入至聚合器中之方法。(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.

(3)將於載體(C)上承載有成分(A)之觸媒成分、成分(B)以任意順序加入至聚合器中之方法。(3) A method in which a catalyst component of the component (A) and a component (B) are carried in a carrier (C) in an arbitrary order.

(4)將於載體(C)上承載有成分(B)之觸媒成分、成分(A)以任意順序加入至聚合器中之方法。(4) A method in which a catalyst component of the component (B) and a component (A) are carried in a carrier (C) in an arbitrary order.

(5)將於載體(C)上承載有成分(A)與成分(B)之觸媒成分加入至聚合器中之方法。(5) A method in which a catalyst component containing a component (A) and a component (B) is carried on a carrier (C) to be added to a polymerization vessel.

上述(2)~(5)各方法中，亦可使各觸媒成分中至少2種以上預先接觸。承載有成分(B)之上述(4)、(5)各方法中，可根據需要以任意順序添加未承載之成分(B)。該情形時成分(B)可相同亦可不同。又，上述於成分(C)上承載有成分(A)之固體觸媒成分、於成分(C)上承載有成分(A)以及成分(B)之固體觸媒成分，係可預先聚合烯烴，亦可於預備聚合之固體觸媒成分上，進而承載觸媒成分。In each of the above methods (2) to (5), at least two or more of the respective catalyst components may be brought into contact in advance. In each of the above methods (4) and (5) in which the component (B) is carried, the unsupported component (B) may be added in an arbitrary order as needed. In this case, the component (B) may be the same or different. Further, the solid catalyst component carrying the component (A) on the component (C) and the solid catalyst component carrying the component (A) and the component (B) on the component (C) are capable of prepolymerizing an olefin. It can also be used to pre-polymerize the solid catalyst component and further carry the catalyst component.

本發明相關之烯烴系聚合體之製造方法中，係於上述烯烴聚合用觸媒之存在下，使烯烴聚合或共聚合而獲得烯烴系聚合體。於本發明中，聚合可以溶液聚合、懸濁聚合等液相聚合法或氣相聚合法之任一者實施。作為液相聚合法中使用之惰性碳氫化合物媒介，具體可列舉丙烷、丁烷、戊烷、己烷、庚烷、辛烷、癸烷、十二烷、燈油等脂肪族烴；環戊烷、環己烷、甲基環戊烷等脂環族烴；苯、甲苯、二甲苯等芳香族烴；氯化乙烯、氯苯、二氯甲烷等鹵化烴或該等之混合物等，烯烴自身亦可作為溶劑使用。In the method for producing an olefin-based polymer according to the present invention, an olefin-based polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization. In the present invention, the polymerization may be carried out by any of a liquid phase polymerization method or a gas phase polymerization method such as solution polymerization or suspension polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; and cyclopentane. An alicyclic hydrocarbon such as cyclohexane or methylcyclopentane; an aromatic hydrocarbon such as benzene, toluene or xylene; a halogenated hydrocarbon such as chlorinated ethylene, chlorobenzene or dichloromethane or a mixture thereof; Can be used as a solvent.

使用如上述之烯烴聚合用觸媒，進行烯烴聚合時，成分(A)通常以每1公升反應容積，使用10－ 8 ~10－ 2 莫耳、較佳10－ 7 ~10－ 3 莫耳之量。成分(B－1)通常以成分(B－1)與成分(A)中全過渡金屬原子(M)之莫耳比[(B－1)/M]為0.01~5,000、較佳0.05~2,000之量使用。成分(B－2)通常以成分(B－2)中鋁原子與成分(A)中全過渡金屬(M)之莫耳比[(B－2)/M]為10~5,000、較佳20~2,000之量使用。成分(B－3)通常以成分(B－3)與成分(A)中過渡金屬原子(M)之莫耳比[(B－3)/M]為1~10、較佳1~5之量使用。When the olefin polymerization is carried out using the catalyst for olefin polymerization as described above, the component (A) is usually used in an amount of from 10 - 8 to 10 - 2 mol, preferably from 10 - 7 to 10 - 3 mol per 1 liter of the reaction volume. the amount. The component (B-1) is usually 0.01 to 5,000, preferably 0.05 to 2,000, in terms of the molar ratio [(B-1)/M] of the total transition metal atom (M) in the component (B-1) and the component (A). The amount used. The component (B-2) is usually 10 to 5,000, preferably 20, in terms of the molar ratio of the aluminum atom in the component (B-2) to the total transition metal (M) in the component (A) [(B-2)/M]. ~2,000 quantities are used. The component (B-3) is usually 1 to 10, preferably 1 to 5, in the molar ratio [(B-3)/M] of the transition metal atom (M) in the component (B-3) and the component (A). The amount is used.

成分(D)係於成分(B)為成分(B－1)之情形時，通常以莫耳比[(D)/(B－1)]為0.01~10、較佳0.1~5之量使用；於成分(B)為成分(B－2)之情形時，通常以莫耳比[(D)/(B－2)]為0.01~2、較佳0.005~1之量使用；於成分(B)為成分(B－3)之情形時，通常以莫耳比[(D)/(B－3)]為0.01~10、較佳0.1~5之量使用。When the component (B) is the component (B-1), the component (D) is usually used in an amount of 0.01 to 10, preferably 0.1 to 5, in terms of a molar ratio [(D)/(B-1)]. When the component (B) is the component (B-2), it is usually used in an amount of 0.01 to 2, preferably 0.005 to 1 in terms of molar ratio [(D)/(B-2)]; When B) is the component (B-3), the molar ratio [(D)/(B-3)] is usually 0.01 to 10, preferably 0.1 to 5.

又，使用此種烯烴聚合用觸媒之烯烴聚合溫度，通常為－50~＋200℃，較佳0~170℃之範圍。聚合壓力通常為常壓~10MPa之計示壓力，較佳常壓~5MPa計示壓力之條件，聚合反應可以分批式、半連續式、連續式任一之方法進行。進而亦可分為反應條件不同之二階段以上而進行聚合。所得之烯烴系聚合體之分子量，可藉由使氫存在於聚合系中，或使聚合溫度變化而進行調節。進而，亦可藉由使用之成分(B)之量而進行調節。添加氫之情形時，其量較適合為每1 kg烯烴為0.001~100 NL左右。Further, the polymerization temperature of the olefin used in the catalyst for olefin polymerization is usually in the range of -50 to +200 ° C, preferably 0 to 170 ° C. The polymerization pressure is usually a gauge pressure of atmospheric pressure ~10 MPa, preferably a pressure of ~5 MPa, and the polymerization reaction can be carried out in batch, semi-continuous or continuous manner. Further, it is also possible to carry out polymerization by dividing into two or more stages in which the reaction conditions are different. The molecular weight of the obtained olefin-based polymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature. Further, it is also possible to adjust by the amount of the component (B) to be used. When hydrogen is added, the amount is preferably about 0.001 to 100 NL per 1 kg of olefin.

於本發明中，供給於聚合反應中之烯烴，為選自乙烯以及α－烯烴之1種以上之單體，較佳為至少1種單體為乙烯或丙烯。作為α－烯烴，可為碳原子數為3~20、較佳3~10之直鏈狀或支鏈狀α－烯烴，例如可列舉：丙烯、1－丁烯、2－丁烯、1－戊烯、3－甲基－1－丁烯、1－己烯、4－甲基－1－戊烯、3－甲基－1－戊烯、1－辛烯、1－癸烯、1－十二烯、1－十四烯、1－十六烯、1－十八烯、1－二十烯等。又，亦可為碳原子數為3~30、較佳3~20之環狀烯烴，例如可列舉：環戊烯、環庚烯、降烯、5－甲基－2－降烯、四環十二烯、2－甲基－1,4,5,8－二甲橋－1,2,3,4,4a,5,8,8a－八氫化萘；極性單體，例如可列舉丙烯酸、甲基丙烯酸、反丁烯二酸、順丁烯二酸酐、衣康酸、衣康酸酐、雙環(2,2,1)－5－庚基－2,3－二羧酸酐等α,β－不飽和羧酸，以及該等之鈉鹽、鉀鹽、鋰鹽、鋅鹽、鎂鹽、鈣鹽、鋁鹽等金屬鹽；丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸2－乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯等之α,β－不飽和羧酸酯；乙酸乙烯酯、丙酸乙烯酯、己酸乙烯酯、癸酸乙烯酯、十二烷酸乙烯酯、硬脂酸乙烯酯、三氟乙酸乙烯酯等乙烯酯類；丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯、衣康酸單環氧丙酯等不飽和環氧丙酯等。又，亦可使乙烯環己烷、二烯或多烯等芳香族乙烯化合物，例如可列舉苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、鄰,對二甲基苯乙烯、鄰乙基苯乙烯、間乙基苯乙烯、對乙基苯乙烯等單或多烷基苯乙烯；甲氧基苯乙烯、乙氧基苯乙烯、乙烯基苯甲酸、乙烯基苯甲酸甲酯、乙烯基苄基乙酸酯、羥基苯乙烯、鄰氯苯乙烯、對氯苯乙烯、二乙烯苯等含有官能基之苯乙烯衍生物；以及3－苯基丙烯，4－苯基丙烯，α－甲基苯乙烯等共存於反應系中進行聚合。In the present invention, the olefin to be supplied to the polymerization reaction is one or more monomers selected from the group consisting of ethylene and an α-olefin, and preferably at least one monomer is ethylene or propylene. The α-olefin may be a linear or branched α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and examples thereof include propylene, 1-butene, 2-butene, and 1- Pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1- Decadiene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like. Further, it may be a cyclic olefin having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and examples thereof include cyclopentene and cycloheptene. Alkene, 5-methyl-2-nor Alkene, tetracyclododecene, 2-methyl-1,4,5,8-dimethyl bridge-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polar monomer, for example Examples thereof include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo(2,2,1)-5-heptyl-2,3-dicarboxylic anhydride. α,β-unsaturated carboxylic acid, and metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt, aluminum salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methyl α,β-unsaturated carboxylic acid esters such as isopropyl acrylate, n-butyl methacrylate and isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl citrate, ten Vinyl esters such as vinyl dialkylate, vinyl stearate, vinyl trifluoroacetate; unsaturated epoxy such as glycidyl acrylate, glycidyl methacrylate, and itaconopropionate Esters and the like. Further, examples of the aromatic vinyl compound such as ethylene cyclohexane, diene or polyene include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, and o-p-dimethylene. Mono- or polyalkylstyrenes such as styrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, vinylbenzene a styrene derivative containing a functional group such as methyl formate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropene, 4-phenyl Propylene, α-methylstyrene, and the like are coexisted in the reaction system to carry out polymerization.

於本發明之烯烴系聚合體之製造方法中，至少1種單體為乙烯或丙烯。單體為二種以上之情形時，較佳係乙烯、丙烯或乙烯＋丙烯為全體單體量之50莫耳%以上，具體而言可較佳地用於乙烯/丙烯共聚體(EPR)、丙烯/乙烯共聚體(PER)、丙烯/乙烯無規共聚體(無規PP)、丙烯/乙烯嵌段共聚體(嵌段PP)、丙烯/丁烯共聚體(PBR)、丙烯/乙烯/丁烯共聚體(PEBR)等之製造中。In the method for producing an olefin-based polymer of the present invention, at least one of the monomers is ethylene or propylene. When two or more monomers are used, ethylene, propylene or ethylene + propylene is preferably 50 mol% or more of the total monomer amount, and specifically, it is preferably used for an ethylene/propylene copolymer (EPR). Propylene/ethylene interpolymer (PER), propylene/ethylene random interpolymer (random PP), propylene/ethylene block copolymer (block PP), propylene/butene interpolymer (PBR), propylene/ethylene/butyl In the manufacture of an olefin copolymer (PEBR) or the like.

以下，根據實施例對本發明加以詳細說明。Hereinafter, the present invention will be described in detail based on examples.

[物性之測定法][Measurement of physical properties] <聚合物中之乙烯含量><ethylene content in the polymer>

使用日本分光公司製造之傅立葉變換紅外分光光度計FT/IR－610，求取基於丙烯之甲基之橫向搖擺振動1155cm－ 1 附近之面積與C－H伸縮振動之諧波吸收4325 cm－ 1 附近之吸光度，由該比以檢量線(使用以1 3 C－NMR標定之標準試料製成)算出。Manufactured by Nippon Bunko, the Fourier transform infrared spectrophotometer FT / IR-610, obtains a lateral rocking vibration based on methyl group of propylene 1155cm - The area near a harmonic of the C-H stretching vibration absorption of 4325 cm - 1 near the absorbance ratio was calculated from the calibration curve (using the calibration standard 1 3 C-NMR sample made).

<極限黏度([η])><limit viscosity ([η])>

使用離合公司製造之自動動黏度測定裝置VMR－053PC以及改良尤伯落德型毛細管黏度計，求得十氫萘、135℃下之比黏度η sp，並以下式算出極限黏度。The specific viscosity of the decahydronaphthalene and the specific viscosity η sp at 135 ° C was determined using an automatic dynamic viscosity measuring device VMR-053PC manufactured by a clutch company and a modified Uberde type capillary viscometer, and the ultimate viscosity was calculated by the following formula.

[η]＝η sp/{C(1＋K．η sp)}<C：溶液濃度[g/dl]，K：常數>[η]=η sp/{C(1+K.η sp)}<C: solution concentration [g/dl], K: constant>

<重量平均分子量(Mw)，數量平均分子量(Mn)><weight average molecular weight (Mw), number average molecular weight (Mn)>

使用Waters公司製造之Alliance GPC2000，以流量1.0 ml/分鐘移動500 μ l之濃度為0.1 wt%之試料溶液，並進行測定。標準聚苯乙烯使用Tosoh公司製造，作為換算為各聚合體之分子量而算出。Using a Alliance GPC2000 manufactured by Waters, 500 μl of a sample solution having a concentration of 0.1 wt% was moved at a flow rate of 1.0 ml/min, and measured. Standard polystyrene was produced by Tosoh Corporation and calculated as the molecular weight of each polymer.

分離管柱：TSKgel GMH6－HT以及TSKgel GMH6－HTL(各內徑7.5 mm，長度300 mm各2根)管柱溫度：140℃移動相：鄰二氯苯檢出器：示差折射器Separation column: TSKgel GMH6-HT and TSKgel GMH6-HTL (each diameter 7.5 mm, length 300 mm each) Column temperature: 140 °C Mobile phase: o-dichlorobenzene detector: differential refractor

以下，根據實施例對本發明加以更詳細之說明，但本發明並非限定於該等實施例者。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.

再者，以合成例所得之化合物之結構，係使用270 MHz1 H－NMR(日本電子GSH－270)，FD－質量分析(日本電子SX－102A)等而測定。In addition, the structure of the compound obtained by the synthesis example was measured using 270 MHz 1 H-NMR (Japan Electronics GSH-270), FD-mass analysis (Japan Electronics SX-102A), and the like.

[實施例1][Example 1] <[1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀]><[1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]茀]>

於氮氣環境下，於300 ml之三口燒瓶中加入25.8 g無水氯化鋁、5.18 g茀、200 ml二硫化碳。於水浴下，以15分鐘滴下6.18 g氧化三甲苯，於迴流下攪拌10小時。放置冷卻後，添加100 ml水，分離有機層。以300 ml己烷萃取水層，與先前之有機層合併，以水、飽和氯化鈉水溶液洗淨，以硫酸鎂乾燥後，餾去溶劑。以管柱層析法進行精製，以乙醇/己烷混合溶劑進行再結晶。收量為1.14 g。以1 H－NMR光譜進行鑒定。以下表示該測定結果。25.8 g of anhydrous aluminum chloride, 5.18 g of hydrazine, and 200 ml of carbon disulfide were placed in a 300 ml three-necked flask under a nitrogen atmosphere. Under a water bath, 6.18 g of xylene oxide was added dropwise over 15 minutes, and the mixture was stirred under reflux for 10 hours. After standing to cool, 100 ml of water was added and the organic layer was separated. The aqueous layer was extracted with 300 ml of hexane, and the organic layer was combined, washed with water and saturated aqueous sodium chloride, and dried over magnesium sulfate. It was purified by column chromatography and recrystallized from a mixed solvent of ethanol/hexane. The yield is 1.14 g. Identification was carried out by 1 H-NMR spectroscopy. The measurement results are shown below.

1 H－NMR(270 MHz,CDCl3 ,TMS基準)：δ 7.62(s,2H),δ 7.43(s,2H),δ 6.03(s,2H),δ 3.89(s,2H),δ 2.19(s,6H),δ 1.33(s,12H) 1 H-NMR (270 MHz, CDCl 3 , TMS basis): δ 7.62 (s, 2H), δ 7.43 (s, 2H), δ 6.03 (s, 2H), δ 3.89 (s, 2H), δ 2.19 ( s,6H),δ 1.33(s,12H)

[實施例2][Embodiment 2] <[(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯]><[(phenyl)(methyl)methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,3,6,8,8-hexamethyl-1H, 8H-dicyclopenta[b,h]fluorenyl)zirconium dichloride]>

(1)3－第三丁基－6－苯基－1,6－二甲基－芙之合成於氮氣環境下，於100 ml之三口燒瓶中加入1.50 g以缽粉碎之氫氧化鉀、0.91 g 18－冠－6－醚、45 ml之THF。於水浴下，以10分鐘滴下2.70 g第三丁基－甲基環戊二烯，攪拌3小時。以10分鐘滴下11.33 g苯乙酮，攪拌22小時。將反應溶液注入至100 ml之2N鹽酸中。分離有機層，以200 ml己烷萃取水層，與先前之有機層合併，以飽和碳酸氫鈉水溶液、水、飽和氯化鈉水溶液洗淨。以硫酸鎂乾燥後，餾去溶劑，以管柱層析法進行精製。收量為1.98 g。以1 H－NMR光譜進行鑒定。以下表示該測定結果。根據1 H－NMR之結果為異構體混合物。(1) Synthesis of 3-tert-butyl-6-phenyl-1,6-dimethyl-fusin In a 100 ml three-necked flask, 1.50 g of hydrazine pulverized potassium hydroxide, 0.91 was added under a nitrogen atmosphere. g 18-crown-6-ether, 45 ml of THF. 2.70 g of tert-butyl-methylcyclopentadiene was added dropwise over 10 minutes under a water bath and stirred for 3 hours. 11.33 g of acetophenone was dropped over 10 minutes and stirred for 22 hours. The reaction solution was poured into 100 ml of 2N hydrochloric acid. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (200 ml), and the organic layer was combined and washed with saturated aqueous sodium hydrogen carbonate, water and saturated aqueous sodium chloride. After drying over magnesium sulfate, the solvent was evaporated and purified by column chromatography. The volume is 1.98 g. Identification was carried out by 1 H-NMR spectroscopy. The measurement results are shown below. The isomer mixture was obtained from the result of 1 H-NMR.

1 H－NMR(270 MHz,CDCl3 ,TMS基準)：δ 7.37－7.30(m,4H),7.24－7.20(m,1H),6.33＋5.56(m＋m,1H),6.17＋6.11(d＋d,1H),2.50＋2.41(s＋s,3H),2.34＋1.36(s＋s,3H),1.19＋1.01(s＋s,9H) 1 H-NMR (270 MHz, CDCl 3 , TMS basis): δ 7.37-7.30 (m, 4H), 7.24-7.20 (m, 1H), 6.33+5.56 (m+m, 1H), 6.17+6.11 (d+d) , 1H), 2.50+2.41 (s+s, 3H), 2.34+1.36 (s+s, 3H), 1.19+1.01 (s+s, 9H)

(2)(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀)之合成於氮氣環境下,於100 ml三口燒瓶中加入1.71 g之1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀、40 ml二乙基醚。冰/丙酮浴下，經3分鐘滴下3.5 ml(5.4 mmol)1.54M之正丁基鋰己烷溶液。一面緩慢升溫至室溫一面攪拌21小時。以10分鐘添加1.41 g(5.92 mmol)3－第三丁基－6－苯基－1,6－二甲基芙之二乙醚溶液。於迴流下攪拌7天後，將反應溶液注入100 ml之1 N鹽酸中。分離有機層，以75 ml己烷萃取水層2次。合併所得之有機層，以飽和碳酸氫鈉水溶液洗淨1次、以水洗淨2次、以飽和食鹽水洗淨1次。以硫酸鎂乾燥，餾去溶劑。所得之固體以管柱層析法精製，以甲醇洗淨。收量為0.70 g。以FD－MS光譜進行鑒定。以下表示其結果。(2) (phenyl) (methyl) methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,3,6,8,8-hexamethyl-1H ,8H-dicyclopenta[b,h]茀) was synthesized under a nitrogen atmosphere, and 1.71 g of 1,1,3,6,8,8-hexamethyl-1H,8H- was added to a 100 ml three-necked flask. Dicyclopenta[b,h]indole, 40 ml of diethyl ether. Under ice/acetone bath, 3.5 ml (5.4 mmol) of a 1.54 M solution of n-butyllithium in hexane was added over 3 minutes. Stir for 21 hours while slowly warming to room temperature. A solution of 1.41 g (5.92 mmol) of 3-tert-butyl-6-phenyl-1,6-dimethyl ketone in diethyl ether was added over 10 minutes. After stirring at reflux for 7 days, the reaction solution was poured into 100 ml of 1 N hydrochloric acid. The organic layer was separated and the aqueous layer was extracted twice with 75 ml of hexane. The obtained organic layer was combined, washed once with a saturated aqueous solution of sodium hydrogencarbonate, twice with water, and once with saturated brine. It was dried over magnesium sulfate, and the solvent was evaporated. The obtained solid was purified by column chromatography and washed with methanol. The yield is 0.70 g. Identification by FD-MS spectroscopy. The results are shown below.

FD－MS：m/Z＝564(M＋ )FD-MS: m/Z=564(M + )

(3)(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯之合成於氮氣環境下，在30 ml Schlenk管中加入0.691 g(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯基)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)、15 ml醚。於醚/丙酮浴下，添加1.75 ml(2.70 mmol)之1.54Mn－BuLi己烷溶液攪拌10分鐘。於室溫下攪拌24小時後，以冰/丙酮浴冷卻後，添加0.439 g(1.88 mmol)四氯化鋯。一面緩慢恢復至室溫一面攪拌19小時。餾去溶劑，以己烷萃取可溶分。餾去溶劑，以醚進行再結晶。將所得之結晶以戊烷洗淨。收量為52 mg。以1 H－NMR光譜、FD－MS進行鑒定。以下表示該測定結果。(3) (phenyl) (methyl) methylene (3-tert-butyl-5-methylcyclopentadienyl) (1,1,3,6,8,8-hexamethyl-1H ,8H-dicyclopenta[b,h]fluorenyl)zirconium dichloride was synthesized under nitrogen atmosphere, adding 0.691 g of (phenyl)(methyl)methylene (3-third) to a 30 ml Schlenk tube. Butyl-5-methylcyclopentadienyl) (1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]decyl), 15 ml of ether. 1.75 ml (2.70 mmol) of a 1.54 Mn-BuLi hexane solution was added for 10 minutes under an ether/acetone bath. After stirring at room temperature for 24 hours, after cooling in an ice/acetone bath, 0.439 g (1.88 mmol) of zirconium tetrachloride was added. Stir for 19 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble fraction was extracted with hexane. The solvent was distilled off and recrystallized from ether. The resulting crystals were washed with pentane. The yield is 52 mg. Identification was carried out by 1 H-NMR spectrum and FD-MS. The measurement results are shown below.

1 H－NMR(270 MHz,CDCl3 ,TMS基準)：δ 7.94－7.90(m,1H),7.87(s,1H),7.85(s,1H),7.82(s,1H),7.76－7.73(m,1H),7.65－7.50(m,1H),7.45－4.38(m,2H),6.09(d,1H),6.03(d,1H),5.90(d,1H),5.90(d,1H,),5.87(d,1H),5.54(d,1H),2.78(s,3H),2.42(s,3H),2.20(d,3H),2.16(d,3H),1.53(s,3H),1.35(s,6H),1.21(s,1H),1.01(s,9H),0.96(s,3H),0.86(s,3H) 1 H-NMR (270 MHz, CDCl 3 , TMS basis): δ 7.94-7.90 (m, 1H), 7.87 (s, 1H), 7.85 (s, 1H), 7.82 (s, 1H), 7.76-7.73 ( m, 1H), 7.65-7.50 (m, 1H), 7.45-4.38 (m, 2H), 6.09 (d, 1H), 6.03 (d, 1H), 5.90 (d, 1H), 5.90 (d, 1H, ), 5.87 (d, 1H), 5.54 (d, 1H), 2.78 (s, 3H), 2.42 (s, 3H), 2.20 (d, 3H), 2.16 (d, 3H), 1.53 (s, 3H) , 1.35 (s, 6H), 1.21 (s, 1H), 1.01 (s, 9H), 0.96 (s, 3H), 0.86 (s, 3H)

FD－MS：m/Z＝724(M＋ )FD-MS: m/Z=724(M + )

[實施例3][Example 3] －承載觸媒之製備－- Preparation of carrier catalyst -

於經充分氮氣置換之100 ml之三口燒瓶中安裝攪拌棒，於其中添加1.00 g二氧化矽承載甲基鋁氧烷(Al＝14.6 wt%)。在此於室溫下添加10 ml脫水甲苯，一面攪拌一面添加20 ml之於上述實施例2中合成之(苯基)(甲基)亞甲基(3－第三丁基－5－甲基環戊二烯)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯21.0mg之甲苯溶液作為過渡金屬化合物，攪拌1小時。以過濾器過濾所得之漿料，並將過濾器上之粉體以10 ml脫水甲苯洗淨1次，繼而以10 ml脫水己烷洗淨3次。將洗淨後之粉體減壓乾燥2小時獲得0.934 g粉體，故將其與8.41 g礦物油相混合而製成10.0 wt%漿料。A stir bar was placed in a 100 ml three-necked flask which was sufficiently purged with nitrogen, and 1.00 g of cerium oxide supported methylaluminoxane (Al = 14.6% by weight) was added thereto. Here, 10 ml of dehydrated toluene was added at room temperature, and 20 ml of (phenyl)(methyl)methylene (3-tert-butyl-5-methyl group) synthesized in the above Example 2 was added while stirring. a cyclopentadienyl (1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorenyl)zirconium dichloride 21.0 mg toluene solution as a transition metal compound Stir for 1 hour. The resulting slurry was filtered through a filter, and the powder on the filter was washed once with 10 ml of dehydrated toluene, followed by washing 3 times with 10 ml of dehydrated hexane. The washed powder was dried under reduced pressure for 2 hours to obtain 0.934 g of a powder, so that it was mixed with 8.41 g of mineral oil to prepare a 10.0 wt% slurry.

[實施例4][Example 4] －丙烯/乙烯共聚合－- propylene/ethylene copolymerization -

於經充分氮氣置換之內容量為2000 ml之SUS製高壓釜中加入300 g液體丙烯，一面充分攪拌一面加溫至55℃，此處以乙烯氣體進行加壓將高壓釜內壓升為30 kg/Cm2 G。繼而，於安裝於高壓釜上、並經充分氮氣置換之內容量30 ml之觸媒插入用壺中添加4 ml脫水己烷與1 ml三異丁基鋁之己烷溶液(Al＝1.0 M)之混合溶液，以氮加壓插入至高壓釜中。繼而於觸媒插入用壺中，添加344 mg上述實施例3中所製備之承載觸媒之漿料與1.0 mmol三異丁基鋁之己烷溶液(Al＝1.0 M)之混合物，以氮加壓插入至高壓釜中開始聚合。聚合進行3分鐘後，添加少量甲醇停止聚合。於添加有鹽酸之大過量甲醇中添加聚合物並脫灰，過濾聚合物後，於80℃下減壓乾燥10小時。所得之聚合物為16.7 g，聚合活性為342 kg－Polymer/mmol－Zr．hr。聚合物分析之結果為：聚合物中之乙烯含量＝30 mol%、[η]＝2.22 dl/g、Mw＝238,000、Mw/Mn＝2.0。300 g of liquid propylene was added to a SUS autoclave with a volume of 2000 ml which was sufficiently nitrogen-substituted, and heated to 55 ° C while being fully stirred. Here, the pressure in the autoclave was increased to 30 kg by pressurization with ethylene gas. Cm 2 G. Then, 4 ml of dehydrated hexane and 1 ml of hexane solution of triisobutylaluminum (Al = 1.0 M) were placed in a catalyst insertion pot installed in an autoclave and sufficiently filled with nitrogen. The mixed solution was inserted into the autoclave under nitrogen pressure. Then, in a pot for catalyst insertion, a mixture of 344 mg of the catalyst-carrying slurry prepared in the above Example 3 and 1.0 mmol of a solution of triisobutylaluminum in hexane (Al = 1.0 M) was added thereto, followed by nitrogen addition. The polymerization was started by press-insertion into an autoclave. After the polymerization was carried out for 3 minutes, a small amount of methanol was added to stop the polymerization. The polymer was added to a large excess of methanol to which hydrochloric acid was added, and degummed. After filtering the polymer, it was dried under reduced pressure at 80 ° C for 10 hours. The obtained polymer was 16.7 g and the polymerization activity was 342 kg-Polymer/mmol-Zr. Hr. The results of the polymer analysis were as follows: ethylene content in the polymer = 30 mol%, [η] = 2.22 dl/g, Mw = 238,000, and Mw / Mn = 2.0.

[實施例5][Example 5] －丙烯/乙烯共聚合－- propylene/ethylene copolymerization -

除了使用347 mg上述實施例3中製備之承載觸媒之漿料，以乙烯氣體進行加壓將高壓釜內壓上升至35 kg/cm2 G，聚合4分鐘以外，其他與上述實施例4相同進行聚合。所得之聚合物為50.9 g，聚合活性為773 kg－Polymer/mmol－Zr．hr。聚合物分析之結果為：聚合物中之乙烯含量＝47 mol%、[η]＝2.55 dl/g、Mw＝250,000、Mw/Mn＝2.0。The same as in the above Example 4, except that 347 mg of the catalyst-carrying slurry prepared in the above Example 3 was used, and the internal pressure of the autoclave was raised to 35 kg/cm 2 G by pressurization with ethylene gas, and polymerization was carried out for 4 minutes. Perform polymerization. The obtained polymer was 50.9 g, and the polymerization activity was 773 kg-Polymer/mmol-Zr. Hr. As a result of the polymer analysis, the ethylene content in the polymer = 47 mol%, [η] = 2.55 dl/g, Mw = 250,000, and Mw / Mn = 2.0.

[實施例6][Embodiment 6] －丙烯/乙烯共聚合－- propylene/ethylene copolymerization -

除了使用199 mg上述實施例3中所製備之承載觸媒之漿料，以乙烯氣體進行加壓將高壓釜內壓上升至40 kg/cm2 G，進行4分鐘聚合以外，其他與上述實施例4相同進行聚合。所得之聚合物為24.3 g，聚合活性為734 kg－Polymer/mmol－Zr．hr。聚合物分析之結果為：聚合物中之乙烯含量＝60 mol%、[η]＝3.04 dl/g、Mw＝305,000、Mw/Mn＝2.1。The same as the above examples except that 199 mg of the catalyst-carrying slurry prepared in the above Example 3 was used, and the internal pressure of the autoclave was raised to 40 kg/cm 2 G by pressurization with ethylene gas for 4 minutes. 4 The same polymerization was carried out. The obtained polymer was 24.3 g and the polymerization activity was 734 kg-Polymer/mmol-Zr. Hr. The results of the polymer analysis were as follows: ethylene content in the polymer = 60 mol%, [η] = 3.04 dl/g, Mw = 305,000, and Mw / Mn = 2.1.

[實施例7][Embodiment 7] －丙烯整體聚合－-Propylene polymerization -

於經充分氮氣置換之50 ml之側臂燒瓶(side arm flask)中加入磁性攪拌子，於其中添加1.02 g上述實施例3中製備之承載觸媒之漿料與1.0 mmol三異丁基鋁之己烷溶液(Al＝1.0 M)以及5.0 ml脫水己烷，並導入至經充分氮氣置換之內容量為2,000 ml之SUS製高壓釜中。其後，加入500 g液體丙烯，於70℃進行40分鐘聚合後，冷卻高壓釜並淨化(purge)丙烯以停止聚合，於80℃下減壓乾燥聚合物10小時。所得之聚合物為248.9 g整規聚丙烯，聚合活性為128.6 kg－PP/mmol－Zr．hr。聚合物分析之結果為：[η]＝3.77 dl/g、Mw＝606,000、Mw/Mn＝2.9、Tm＝147.4℃。A magnetic stirrer was added to a 50 ml side arc flask which was sufficiently nitrogen-substituted, and 1.02 g of the catalyst-carrying slurry prepared in the above Example 3 and 1.0 mmol of triisobutylaluminum were added thereto. A hexane solution (Al = 1.0 M) and 5.0 ml of dehydrated hexane were introduced into a SUS autoclave having a sufficient nitrogen content of 2,000 ml. Thereafter, 500 g of liquid propylene was added, and after polymerization at 70 ° C for 40 minutes, the autoclave was cooled and propylene was purged to stop the polymerization, and the polymer was dried under reduced pressure at 80 ° C for 10 hours. The obtained polymer was 248.9 g of regular polypropylene, and the polymerization activity was 128.6 kg-PP/mmol-Zr. Hr. The results of the polymer analysis were as follows: [η] = 3.77 dl/g, Mw = 606,000, Mw/Mn = 2.9, and Tm = 147.4 °C.

[實施例8][Embodiment 8] －丙烯整體聚合－-Propylene polymerization -

除了使用0.340 g上述實施例3中製備之承載觸媒之漿料，加入500 g液體丙烯後，添加0.30 N1氫以外，其他與實施例7同樣進行聚合。所得之聚合物為328.9 g整規聚丙烯，聚合活性為510.0 kg－PP/mmol－Zr．hr。聚合物分析之結果為：[η]＝2.18 dl/g、Mw＝261,000、Mw/Mn＝2.7、Tm＝150.1℃。The polymerization was carried out in the same manner as in Example 7 except that 0.340 g of the catalyst-carrying slurry prepared in the above Example 3 was used, 500 g of liquid propylene was added, and 0.30 N1 of hydrogen was added thereto. The obtained polymer was 328.9 g of regular polypropylene, and the polymerization activity was 510.0 kg-PP/mmol-Zr. Hr. The results of the polymer analysis were as follows: [η] = 2.18 dl/g, Mw = 261,000, Mw / Mn = 2.7, and Tm = 150.1 °C.

[實施例9][Embodiment 9] －丙烯整體聚合－-Propylene polymerization -

除了使用0.201 g上述實施例3中製備之承載觸媒之漿料，加入500 g液體丙烯後，添加0.60 N1氫以外，其他與實施例7相同進行聚合。所得之聚合物為255.0 g整規聚丙烯，聚合活性為670.2 kg－PP/mmol－Zr．hr。聚合物分析之結果為：[η]＝1.16 dl/g、Mw＝121,000、Mw/Mn＝2.3、Tm＝150.3℃。The polymerization was carried out in the same manner as in Example 7 except that 0.201 g of the catalyst-carrying slurry prepared in the above Example 3 was used, 500 g of liquid propylene was added, and 0.60 N1 of hydrogen was added. The obtained polymer was 255.0 g of regular polypropylene, and the polymerization activity was 670.2 kg-PP/mmol-Zr. Hr. The results of the polymer analysis were as follows: [η] = 1.16 dl/g, Mw = 121,000, Mw/Mn = 2.3, and Tm = 150.3 °C.

[實施例10][Embodiment 10] <二－對甲苯基亞甲基(環戊二烯基(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯><Di-p-tolylmethylene (cyclopentadienyl (1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorenyl) dichloride Zirconium>

(1)6,6－二－對甲苯基芙之合成於氮氣環境下，於具有磁性攪拌子以及三通旋塞之200 ml二口燒瓶中加入6.72 g(31.9 mmol)4,4’－二甲基二苯甲酮、30 ml四氫呋喃。一面以冰水浴冷卻一面緩慢添加19 ml(38 mmol)之2.0 mol/l環戊二烯基鈉/四氫呋喃溶液後，於室溫下攪拌6天。一面以冰水浴冷卻一面緩慢添加100ml 1N之鹽酸，繼而添加100 ml二乙基醚。分離有機層，以100 ml水洗淨2次，以100 ml飽和食鹽水洗淨1次。以硫酸鎂乾燥後，餾去溶劑，以管柱層析法進行精製。收量為6.15 g，收率為74.5%。以1 H－NMR光譜進行鑒定。以下表示該測定結果。(1) Synthesis of 6,6-di-p-tolylfufu In a 200 ml two-necked flask with a magnetic stir bar and a three-way cock, 6.72 g (31.9 mmol) of 4,4'-dimethyl was added under a nitrogen atmosphere. Benzophenone, 30 ml tetrahydrofuran. While slowly cooling the ice water bath, 19 ml (38 mmol) of a 2.0 mol/l sodium cyclopentadienyl/tetrahydrofuran solution was added, followed by stirring at room temperature for 6 days. While cooling with an ice water bath, 100 ml of 1N hydrochloric acid was slowly added, followed by the addition of 100 ml of diethyl ether. The organic layer was separated, washed twice with 100 ml of water, and washed once with 100 ml of brine. After drying over magnesium sulfate, the solvent was evaporated and purified by column chromatography. The yield was 6.15 g and the yield was 74.5%. Identification was carried out by 1 H-NMR spectroscopy. The measurement results are shown below.

1 H－NMR光譜(270 MHz，CDCl3 ，TMS基準)：d2.39(s,6H),6.2－6.3(m,2H),6.5－6.6(m,2H),7.1－7,2(m,2H) 1 H-NMR spectrum (270 MHz, CDCl 3 , TMS basis): d2.39 (s, 6H), 6.2-6.3 (m, 2H), 6.5-6.6 (m, 2H), 7.1-7, 2 (m) , 2H)

(2)(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)(環戊二烯基)二－對甲苯基甲烷之合成於氮氣環境下，於具有磁性攪拌子、三通旋塞以及50 ml滴下漏斗之200 ml二口燒瓶中，裝入749 mg(2.29 mmol)1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀、30 ml四氫呋喃。一面以冰水浴冷卻一面緩慢添加1.56 ml(2.43 mmol)1.56mol/l之正丁基鋰/己烷溶液後，於室溫下攪拌6.5小時後。一面以甲醇/乾冰浴冷卻，一面使用滴下漏斗以20分鐘緩慢添預先溶解於30 ml四氫呋喃中之6,6－二－對甲苯基芙718 mg(2.78 mmol)。此後緩慢升溫至室溫，於室溫下攪拌20小時。緩慢添加50 ml之1 N鹽酸，繼而添加50 ml二乙基醚。分離有機層，以50 ml水洗淨2次，以50 ml飽和食鹽水洗淨1次，以硫酸鎂乾燥後，餾去溶劑，以管柱層析法進行精製。收量為397 mg(0.679 mmol)，收率為29.6%。以1 H－NMR光譜以及FD－MS光譜進行鑒定。以下表示該測定結果。(2) Synthesis of (1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorenyl)(cyclopentadienyl)di-p-tolylethane 749 mg (2.29 mmol) 1,1,3,6,8,8-hexamethyl was placed in a 200 ml two-necked flask with a magnetic stir bar, a three-way cock and a 50 ml dropping funnel under nitrogen. -1H,8H-dicyclopenta[b,h]indole, 30 ml of tetrahydrofuran. 1.56 ml (2.43 mmol) of a 1.56 mol/l n-butyllithium/hexane solution was slowly added while cooling in an ice water bath, and the mixture was stirred at room temperature for 6.5 hours. While cooling in a methanol/dry ice bath, 6,6-di-p-tolyl 718 mg (2.78 mmol) previously dissolved in 30 ml of tetrahydrofuran was slowly added using a dropping funnel over 20 minutes. Thereafter, the temperature was slowly raised to room temperature, and stirred at room temperature for 20 hours. Slowly add 50 ml of 1 N hydrochloric acid followed by 50 ml of diethyl ether. The organic layer was separated, washed twice with 50 ml of water, and washed once with 50 ml of brine, dried over magnesium sulfate, and then evaporated to the solvent and purified by column chromatography. The yield was 397 mg (0.679 mmol) and the yield was 29.6%. The identification was carried out by 1 H-NMR spectrum and FD-MS spectrum. The measurement results are shown below.

1 H－NMR光譜(270 MHz，CDCl3 ，TMS基準)：0.8－1.4(m,12H),1.8－2.2(m,6H),2.2－2.3(m,6H),2.8－3.1(br,1H),5.33(s,1H),5.9－6.0(m,2H),6.0－6.6(br,4H),6.7－7.5(br,12H) 1 H-NMR spectrum (270 MHz, CDCl 3 , TMS basis): 0.8-1.4 (m, 12H), 1.8-2.2 (m, 6H), 2.2-2.3 (m, 6H), 2.8-3.1 (br, 1H) ), 5.33 (s, 1H), 5.9-6.0 (m, 2H), 6.0-6.6 (br, 4H), 6.7-7.5 (br, 12H)

FD－MS：M/z 584(M＋ )FD-MS: M/z 584 (M + )

(3)二－對甲苯基亞甲基(環戊二烯基(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯之合成於氮氣環境下，於具有磁性攪拌子之100 ml克而達(kjeldahl)燒瓶中，添加376 mg(0.643 mmol)之1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)(環戊二烯基)二－對甲苯基甲烷、40 ml二乙醚。一面以冰水浴冷卻，一面緩慢添加0.86 ml(1.3 mmol)之1.56mol/l正丁基鋰/己烷溶液後，於氮氣環境下以室溫攪拌20小時。一面以甲醇/乾冰浴冷卻一面添加0.260 g(0.688 mmol)四氯化鋯．四氫呋喃錯合物(1：2)後，緩慢升溫至室溫，於室溫下攪拌17小時。於減壓條件下餾去溶劑並以己烷萃取所得之固體，於減壓條件下餾去所得之溶液溶劑。將其以戊烷洗淨後，以二氯甲烷萃取，於減壓條件下餾去所得之溶液溶劑並獲得目標化合物。收量為149 mg(0.200 mmol)，收率為31.1%。以1 H－NMR光譜以及FD－MS光譜進行鑒定。以下表示該測定結果。(3) Di-p-tolylmethylene (cyclopentadienyl (1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]decyl)) The synthesis of zirconium chloride was carried out in a 100 ml gram (kjeldahl) flask with a magnetic stirrer, and 376 mg (0.643 mmol) of 1,1,3,6,8,8-hexamethyl was added. -1H,8H-dicyclopenta[b,h]fluorenyl)(cyclopentadienyl)di-p-tolylethane, 40 ml of diethyl ether. While cooling with an ice water bath, 0.86 ml (1.3 mmol) of a 1.56 mol/l n-butyllithium/hexane solution was slowly added, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere. Add 0.260 g (0.688 mmol) of zirconium tetrachloride on one side while cooling on a methanol/dry ice bath. After the tetrahydrofuran complex (1:2), the mixture was slowly warmed to room temperature and stirred at room temperature for 17 hours. The solvent was distilled off under reduced pressure, and the obtained solid was extracted with hexane, and the obtained solvent was evaporated under reduced pressure. After washing with pentane, it was extracted with dichloromethane, and the obtained solvent was evaporated under reduced pressure to give the title compound. The yield was 149 mg (0.200 mmol) and the yield was 31.1%. The identification was carried out by 1 H-NMR spectrum and FD-MS spectrum. The measurement results are shown below.

1 H－NMR光譜(270 MHz，CDCl3 ，TMS基準)：0.94(s,6H),1.04(s,6H),2.17(d,6H),2.35(s,6H),5.68(t,2H),5.95(d,2H),6.10(s,Ar(Flu),2H),6.28(t,2H),7.1－7.3(m,4H),7.8－7.9(m,4H),7.91(s,2H) 1 H-NMR spectrum (270 MHz, CDCl 3 , TMS basis): 0.94 (s, 6H), 1.04 (s, 6H), 2.17 (d, 6H), 2.35 (s, 6H), 5.68 (t, 2H) , 5.95 (d, 2H), 6.10 (s, Ar (Flu), 2H), 6.28 (t, 2H), 7.1-7.3 (m, 4H), 7.8-7.9 (m, 4H), 7.91 (s, 2H) )

FD－MS：M/z 744(M＋ )FD-MS: M/z 744 (M + )

[實施例11][Example 11] －承載觸媒之製備－- Preparation of carrier catalyst -

於經充分氮氣置換之100 ml之三口燒瓶中安裝攪拌棒，於其中添加0.989 g二氧化矽承載甲基鋁氧烷(Al＝19.3wt%)以及42 ml甲苯。緩慢添加於8.0 ml甲苯中溶解有20.2 mg(0.0271 mmol)作為過渡金屬化合物之上述實施例10中合成之二－對甲苯基亞甲基(環戊二烯基(1,1,3,6,8,8－六甲基－1H,8H－二環戊[b,h]茀基)二氯化鋯之溶液，其後於室溫下攪拌1小時。停止攪拌靜置後，傾析去除上清液。其後，進行3次添加45 ml庚烷、攪拌、靜置、傾析去除上清液之操作。進而添加庚烷，製成全量為50 ml之漿料。一面攪拌一面添加2.0 ml(Al＝2.0 mmol)之三異丁基鋁之正癸烷溶液後，將乙烯吹入漿料中，於20℃下進行34分鐘聚合。停止供給乙烯以及攪拌並靜置後，傾析去除上清液。其後，進行3次添加45 ml庚烷、攪拌、靜置、傾析去除上清液之操作。繼而添加庚烷製成全量為100 ml之漿料，獲得前聚合承載觸媒之庚烷漿料。A stir bar was placed in a 100 ml three-necked flask which was sufficiently purged with nitrogen, to which 0.989 g of cerium oxide-supported methylaluminoxane (Al = 19.3 wt%) and 42 ml of toluene were added. The bis-p-tolylmethylidene (cyclopentadienyl group (1,1,3,6) synthesized in the above Example 10 was slowly added to 8.0 ml of toluene dissolved in 20.2 mg (0.0271 mmol) as a transition metal compound. a solution of 8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorenyl)zirconium dichloride, followed by stirring at room temperature for 1 hour. After stopping the stirring, the mixture was decanted and removed. After that, the operation was carried out by adding 45 ml of heptane three times, stirring, standing, and decanting to remove the supernatant. Further, heptane was added to prepare a slurry having a total amount of 50 ml. 2.0 ml was added while stirring. After (Al = 2.0 mmol) of a solution of triisobutylaluminum in n-decane, ethylene was blown into the slurry and polymerization was carried out at 20 ° C for 34 minutes. The supply of ethylene was stopped, stirred and allowed to stand, and then decanted and removed. After that, the operation of adding 45 ml of heptane, stirring, standing, and decanting to remove the supernatant was carried out three times, and then heptane was added to prepare a slurry having a total amount of 100 ml to obtain a prepolymerization-carrying catalyst. Heptane slurry.

[實施例12][Embodiment 12] －乙烯均聚合－- ethylene homopolymerization -

於經充分氮氣置換之內容積1公升之SUS製高壓釜中加入500 ml精製庚烷，流通乙烯，以乙烯使液相以及氣相飽和。繼而，使用氫－乙烯混合氣體(氫濃度：0.99 vol%)，置換系內氣體後，順次添加0.25 mmol三異丁基鋁、5.0 ml以實施例11製備之承載觸媒漿料。升溫至80℃，以0.78 MPa．G聚合1小時。將所得之聚合物真空乾燥10小時，獲得56.7 g乙烯聚合體。聚合活性為1120 g－PE/g－cat．h。又，所得之乙烯聚合體之[η]為0.88 dl/g。500 ml of purified heptane was placed in a 1 liter SUS autoclave which was sufficiently nitrogen-substituted, and ethylene was passed therethrough to saturate the liquid phase and the gas phase with ethylene. Then, after replacing the internal gas with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.99 vol%), 0.25 mmol of triisobutylaluminum and 5.0 ml of the supported catalyst slurry prepared in Example 11 were sequentially added. Warm up to 80 ° C, to 0.78 MPa. G was polymerized for 1 hour. The obtained polymer was vacuum dried for 10 hours to obtain 56.7 g of an ethylene polymer. The polymerization activity is 1120 g-PE/g-cat. h. Further, [η] of the obtained ethylene polymer was 0.88 dl/g.

[實施例13][Example 13] －乙烯/1－己烯共聚合－-ethylene/1-hexene copolymerization -

於經充分氮氣置換之內容積1公升之SUS製高壓釜中添加500 mL精製庚烷，流通乙烯，以乙烯使液相以及氣相飽和。繼而，順次加入0.25 mmol三異丁基鋁、3.0 ml 1－己烯、1.4 ml以實施例11製備之承載觸媒漿料。升溫至80℃，於0.78MPa．G下進行45分鐘聚合。將所得之聚合物真空乾燥10小時，獲得74.7 g乙烯/1－己烯共聚體。聚合活性為7060 g－PE/g－cat．h。又，所得之乙烯聚合體之密度為0.946 g/cm3 。500 mL of purified heptane was added to a 1 liter autoclave made of SUS, which was sufficiently nitrogen-substituted, and ethylene was passed through, and the liquid phase and the gas phase were saturated with ethylene. Then, 0.25 mmol of triisobutylaluminum, 3.0 ml of 1-hexene, and 1.4 ml of the supported catalyst slurry prepared in Example 11 were sequentially added. Warm up to 80 ° C, at 0.78MPa. Polymerization was carried out for 45 minutes under G. The obtained polymer was vacuum dried for 10 hours to obtain 74.7 g of an ethylene/1-hexene copolymer. The polymerization activity is 7060 g-PE/g-cat. h. Further, the obtained ethylene polymer had a density of 0.946 g/cm 3 .

[比較例1][Comparative Example 1] －承載觸媒之製備－- Preparation of carrier catalyst -

於經充分氮氣置換之100 ml之三口燒瓶中安裝攪拌棒，並於其中加入1.01 g二氧化矽承載甲基鋁氧烷(Al＝14.6 wt%)。此時於室溫下添加10 ml脫水甲苯，一面攪拌一面添加20 ml作為過渡金屬化合物之依據WO01/27124合成之20.6 mg亞異丙基(3－第三丁基－5－甲基環戊二烯基)(茀基)二氯化鋯之甲苯溶液，攪拌1小時。使用過濾器過濾所得之漿料，將過濾器上之粉體以10 ml脫水甲苯洗淨1次，繼而以10 ml脫水己烷洗淨3次。減壓乾燥洗淨後之粉體2小時獲得0.929 g粉體，並將其與8.36 g礦物油相混合製成10.0 wt%漿料。A stir bar was placed in a 100 ml three-necked flask which was sufficiently purged with nitrogen, and 1.01 g of cerium oxide-supported methylaluminoxane (Al = 14.6% by weight) was added thereto. At this time, 10 ml of dehydrated toluene was added at room temperature, and 20 ml of isopropylidene (3-tert-butyl-5-methylcyclopentane) synthesized according to WO01/27124 was added as a transition metal compound while stirring. Alkenyl) (indenyl) zirconium dichloride in toluene solution, stirred for 1 hour. The resulting slurry was filtered using a filter, and the powder on the filter was washed once with 10 ml of dehydrated toluene, followed by washing 3 times with 10 ml of dehydrated hexane. The washed powder was dried under reduced pressure for 2 hours to obtain 0.929 g of a powder, which was mixed with 8.36 g of mineral oil to prepare a 10.0 wt% slurry.

[比較例2][Comparative Example 2] －丙烯/乙烯共聚合－- propylene/ethylene copolymerization -

於經充分氮氣置換之內容量2000 ml之SUS製高壓釜中加入300 g液體丙烯，一面充分攪拌一面升溫至55℃，此時以乙烯氣體進行加壓將高壓釜內壓上升至35 kg/cm2 G。繼而，於安裝於高壓釜上並經充分氮氣置換之內容量30 ml之觸媒插入用壺中加入4 ml脫水己烷與1 ml三異丁基鋁之己烷溶液(Al＝1.0 M)之混合溶液，以氮加壓插入高壓釜中。繼而於觸媒插入用壺中加入170 mg上述比較例1中製備之承載觸媒漿料與1.0 mmol三異丁基鋁之己烷溶液(Al＝1.0 M)之混合物，以氮加壓插入至高壓釜中並開始聚合。進而聚合5分鐘後，添加少量甲醇停止聚合。於添加鹽酸之大過量甲醇中添加聚合物並脫灰，過濾聚合物後，以80℃進行減壓乾燥10小時。所得之聚合物為19.6 g，聚合活性為174 kg－Polymer/mmol－Zr．hr。聚合物分析之結果為：聚合物中乙烯含量＝39 mol%、[η]＝1.00 dl/g、Mw＝74,000、Mw/Mn＝2.0。300 g of liquid propylene was added to a SUS autoclave having a content of 2000 ml which was sufficiently purged with nitrogen, and the temperature was raised to 55 ° C while stirring well. At this time, the internal pressure of the autoclave was raised to 35 kg/cm by pressurization with ethylene gas. 2 G. Then, 4 ml of dehydrated hexane and 1 ml of a hexane solution of triisobutylaluminum (Al = 1.0 M) were placed in a catalyst insertion kettle installed in an autoclave and filled with a sufficient nitrogen content of 30 ml. The solution was mixed and pressurized into the autoclave with nitrogen. Then, a mixture of 170 mg of the catalyst mixture prepared in the above Comparative Example 1 and 1.0 mmol of a solution of triisobutylaluminum in hexane (Al = 1.0 M) was added to the catalyst insertion pot, and the mixture was inserted under pressure with nitrogen. The polymerization was started in the autoclave. After further polymerization for 5 minutes, a small amount of methanol was added to stop the polymerization. The polymer was added to a large excess of methanol to which hydrochloric acid was added, and the mixture was delimed. After filtering the polymer, the mixture was dried under reduced pressure at 80 ° C for 10 hours. The obtained polymer was 19.6 g and the polymerization activity was 174 kg-Polymer/mmol-Zr. Hr. The results of the polymer analysis were as follows: ethylene content in the polymer = 39 mol%, [η] = 1.00 dl/g, Mw = 74,000, and Mw / Mn = 2.0.

[比較例3][Comparative Example 3] －丙烯整體聚合－-Propylene polymerization -

於經充分氮氣置換之50 ml側臂燒瓶中加入磁性攪拌子，並於其中加入0.262 g上述比較例1中製備之承載觸媒漿料與1.0 mmol三異丁基鋁之己烷溶液(Al＝1.0 M)以及5.0 ml脫水己烷，導入經充分氮氣置換之內容量2,000 ml之SUS製高壓釜中。此後，加入500 g液體丙烯後，添加0.30 Nl氫原子，於70℃下聚合40分鐘後，冷卻高壓釜並淨化丙烯以停止聚合。於80℃下減壓乾燥聚合物10小時。所得之聚合物為171.1 g整規聚丙烯，聚合活性為246 kg－PP/mmol－Zr．hr。聚合物分析之結果為：[η]＝1.67 dl/g、Mw＝198000、Mw/Mn＝2.2、Tm＝242.3℃。A magnetic stirrer was placed in a 50 ml side-arm flask which was sufficiently purged with nitrogen, and 0.262 g of the supported catalyst slurry prepared in the above Comparative Example 1 and 1.0 mmol of a solution of triisobutylaluminum in hexane were added thereto (Al = 1.0 M) and 5.0 ml of dehydrated hexane were introduced into a SUS autoclave having a content of 2,000 ml which was sufficiently nitrogen-substituted. Thereafter, after adding 500 g of liquid propylene, 0.30 N of hydrogen atom was added, and after polymerization at 70 ° C for 40 minutes, the autoclave was cooled and propylene was purified to stop the polymerization. The polymer was dried under reduced pressure at 80 ° C for 10 hours. The obtained polymer was 171.1 g of atactic polypropylene with a polymerization activity of 246 kg-PP/mmol-Zr. Hr. The results of the polymer analysis were as follows: [η] = 1.67 dl/g, Mw = 198,000, Mw/Mn = 2.2, and Tm = 242.3 °C.

(產業上之可利用性)(industrial availability)

本發明之在3,6位上取代碳－碳不飽和鍵結之茀化合物、具有含對應於該茀化合物之茀基之配位基的有用且新穎的過渡金屬化合物，係可作為新穎具有用之烯烴聚合用觸媒成分。含有該過渡金屬化合物之烯烴聚合用觸媒為非常高活性，而提供一種更經濟地製造烯烴系共聚體的方法。The present invention is a novel and useful transition metal compound having a carbon-carbon unsaturated bond at the 3,6 position and a ligand having a thiol group corresponding to the fluorene compound. A catalyst component for olefin polymerization. The catalyst for olefin polymerization containing the transition metal compound is very highly active, and provides a method for producing an olefin-based copolymer more economically.

Claims (6)

一種過渡金屬化合物，其特徵為，係以下述通式[Ⅲ]所示： (式中，R23 、R24 、R25 、R26 、R27 、R28 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，可分別相同亦可不同，R23 至R28 之相鄰接之取代基亦可相互鍵結形成環；M為第4族過渡金屬，Y為碳原子，Q為可自鹵素、烴基、陰離子配位基或可以孤立電子對配位之中性配位基選擇相同或不同之組合，j為1~4之整數；Z為自通式[I]所表示之茀衍生物，去除R1 、R2 而衍生之具有2價游離原子價之亞茀基，或去除2個通式[Ⅱ]所表示之茀衍生物之10位之氫原子而衍生之具有2價游離原子價之亞茀基；) (式中，R1 、R2 、R3 、R5 、R6 、R7 、R8 、R9 、R10 、R11 、R12 、R14 係選自氫、烴基、含矽基，且可分別相同亦可不同；R4 、R13 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，且可分別相同亦可不同；R1 至R14 之相鄰接之取代基亦可相互鍵結形成環；又，R4 與R5 可成為一體形成2價取代基之Ra，R12 與R13 亦可成為一體形成2價取代基之Rb；Ra、Rb為選自烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基之除了伸乙烯基以外之2價取代基；) (式中，R15 、R16 、R17 、R18 、R19 、R20 、R21 、R22 係選自氫、烴基、含矽基、含硫基、含氧基、含氮基、含鹵素基，可分別相同亦可不同；或R15 、R16 、R18 、R19 、R21 、R22 為甲基，R17 、R20 為氫原子)。A transition metal compound characterized by the following formula [III]: (wherein R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are selected from the group consisting of hydrogen, a hydrocarbyl group, a mercapto group, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, and a halogen-containing group, respectively The same or different, the adjacent substituents of R 23 to R 28 may also be bonded to each other to form a ring; M is a Group 4 transition metal, Y is a carbon atom, and Q is a halogen-, hydrocarbon-based, anionic ligand. Alternatively, the same or different combinations of the ligand-neutral neutral ligands may be selected, and j is an integer from 1 to 4; Z is an anthracene derivative represented by the general formula [I], and R 1 and R 2 are removed. a mercapto group having a divalent free valence derived from a fluorenylene group having a divalent free valence of 2 or a dehydration of a hydrogen atom at position 10 of the anthracene derivative represented by the general formula [II]; (wherein R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 14 are selected from the group consisting of hydrogen, a hydrocarbon group, and a mercapto group. And may be the same or different; R 4 and R 13 are selected from the group consisting of hydrogen, a hydrocarbon group, a mercapto group, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, a halogen-containing group, and may be the same or different; R 1 The adjacent substituents to R 14 may be bonded to each other to form a ring; further, R 4 and R 5 may form Ra which forms a divalent substituent, and R 12 and R 13 may be integrally formed to form a divalent substituent. Rb; Ra, Rb is a divalent substituent selected from a hydrocarbon group, a mercapto group, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, and a halogen-containing group other than a vinyl group; (wherein R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are selected from the group consisting of hydrogen, a hydrocarbon group, a mercapto group, a sulfur-containing group, an oxygen-containing group, a nitrogen-containing group, The halogen-containing groups may be the same or different; or R 15 , R 16 , R 18 , R 19 , R 21 and R 22 are a methyl group, and R 17 and R 20 are a hydrogen atom). 如申請專利範圍第1項之過渡金屬化合物，其中，上述通式[Ⅲ]中，R24 、R26 為氫。The transition metal compound according to claim 1, wherein in the above formula [III], R 24 and R 26 are hydrogen. 一種烯烴聚合用觸媒，其特徵為，含有申請專利範圍第1或2項之過渡金屬化合物。A catalyst for olefin polymerization, which comprises a transition metal compound according to claim 1 or 2. 一種烯烴聚合用觸媒，其特徵為，至少含有一種自以下選擇之化合物： (A)申請專利範圍第1或2項之過渡金屬化合物；與(B)(B-1)有機金屬化合物；(B-2)有機鋁氧化物化合物；(B-3)與過渡金屬化合物(A)反應而形成離子對之化合物。A catalyst for olefin polymerization, characterized in that it contains at least one compound selected from the following: (A) Transition metal compound of claim 1 or 2; and (B) (B-1) organometallic compound; (B-2) organoaluminum oxide compound; (B-3) and transition metal compound ( A) A compound which reacts to form an ion pair. 一種烯烴系聚合體之製造方法，其係於申請專利範圍第3或4項之烯烴聚合用觸媒存在下，使選自乙烯以及α-烯烴之1種以上單體進行聚合的方法，其中，至少1種單體為乙烯或丙烯。A method for producing an olefin-based polymer, which is a method for polymerizing one or more monomers selected from the group consisting of ethylene and an α-olefin in the presence of a catalyst for olefin polymerization according to the third or fourth aspect of the invention. At least one monomer is ethylene or propylene. 如申請專利範圍第5項之烯烴系聚合體之製造方法，其中，上述通式[Ⅲ]所表示之過渡金屬化合物係以支持於支持體上之形態而使用。The method for producing an olefin-based polymer according to the fifth aspect of the invention, wherein the transition metal compound represented by the above formula [III] is used in a form supported on a support.
TW095118610A 2005-05-25 2006-05-25 Transition metal compound, olefin polymerization catalyst and process for producing olefin polymer TWI396700B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005152873 2005-05-25

Publications (2)

Publication Number Publication Date
TW200708531A TW200708531A (en) 2007-03-01
TWI396700B true TWI396700B (en) 2013-05-21

Family

ID=37452032

Family Applications (1)

Application Number Title Priority Date Filing Date
TW095118610A TWI396700B (en) 2005-05-25 2006-05-25 Transition metal compound, olefin polymerization catalyst and process for producing olefin polymer

Country Status (7)

Country Link
US (1) US7834204B2 (en)
EP (1) EP1900715B1 (en)
JP (1) JP5153326B2 (en)
KR (1) KR100948728B1 (en)
CN (1) CN101180249B (en)
TW (1) TWI396700B (en)
WO (1) WO2006126608A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101370245B1 (en) * 2006-05-23 2014-03-05 린텍 가부시키가이샤 Adhesive composition, adhesive sheet and production process for semiconductor device
KR20080047990A (en) * 2006-11-27 2008-05-30 린텍 가부시키가이샤 Adhesive composition, adhesive sheet and production process for semiconductor device
KR101853875B1 (en) * 2011-06-22 2018-05-03 삼성디스플레이 주식회사 Heterocyclic compound and organic light emitting device containing same
JP6227457B2 (en) * 2014-03-28 2017-11-08 三井化学株式会社 Fluorene compound, transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer
US20160379828A1 (en) * 2015-06-26 2016-12-29 Anil U. Mane Silicon doping source films by ald deposition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1327448A (en) * 1999-10-08 2001-12-19 三井化学株式会社 Metallocene compound, process for producing metallocene compound, olefin polymerization catalyst, polyolefin and process for producing polyolefin
JP2005513713A (en) * 2001-12-12 2005-05-12 キヤノン株式会社 [5] -Helicene and dibenzofluorene materials for use in organic light emitting devices

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3907965A1 (en) 1989-03-11 1990-09-13 Hoechst Ag METHOD FOR PRODUCING A SYNDIOTACTIC POLYOLEFIN
US5036034A (en) 1989-10-10 1991-07-30 Fina Technology, Inc. Catalyst for producing hemiisotactic polypropylene
US5466766A (en) 1991-05-09 1995-11-14 Phillips Petroleum Company Metallocenes and processes therefor and therewith
US5710224A (en) 1991-07-23 1998-01-20 Phillips Petroleum Company Method for producing polymer of ethylene
US5416228A (en) 1991-10-07 1995-05-16 Fina Technology, Inc. Process and catalyst for producing isotactic polyolefins
JP3978798B2 (en) 1996-01-25 2007-09-19 東ソー株式会社 Transition metal compound, olefin polymerization catalyst comprising the same, and method for producing olefin polymer using the same
EP0786466B1 (en) 1996-01-25 2003-04-16 Tosoh Corporation Olefin polymerisation process which comprises a transition metal catalyst.
JP3624989B2 (en) 1996-03-13 2005-03-02 株式会社リコー Optical recording medium
EP0881236A1 (en) 1997-05-26 1998-12-02 Fina Research S.A. Metallocene catalyst component for use in producing isotactic polyolefins
JPH11228588A (en) 1998-02-18 1999-08-24 Mitsui Chem Inc New metallocene compound and polymerization of olefin by using the same
JP4463446B2 (en) 2001-08-07 2010-05-19 三井化学株式会社 Polyolefin resin composition
JP2004149673A (en) * 2002-10-30 2004-05-27 Mitsui Chemicals Inc Method for producing ethylene-based wax

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1327448A (en) * 1999-10-08 2001-12-19 三井化学株式会社 Metallocene compound, process for producing metallocene compound, olefin polymerization catalyst, polyolefin and process for producing polyolefin
JP2005513713A (en) * 2001-12-12 2005-05-12 キヤノン株式会社 [5] -Helicene and dibenzofluorene materials for use in organic light emitting devices

Also Published As

Publication number Publication date
EP1900715A4 (en) 2010-10-06
CN101180249A (en) 2008-05-14
KR20080018208A (en) 2008-02-27
WO2006126608A1 (en) 2006-11-30
CN101180249B (en) 2012-06-20
JP5153326B2 (en) 2013-02-27
KR100948728B1 (en) 2010-03-22
JPWO2006126608A1 (en) 2008-12-25
US20090253876A1 (en) 2009-10-08
EP1900715B1 (en) 2015-04-22
TW200708531A (en) 2007-03-01
EP1900715A1 (en) 2008-03-19
US7834204B2 (en) 2010-11-16

Similar Documents

Publication Publication Date Title
JP4367686B2 (en) Bridged metallocene compound for olefin polymerization and olefin polymerization method using the same
TWI252854B (en) Crosslinked metallocene compound for olefin polymerization and olefin polymerization process using the same
JP4823071B2 (en) Organometallic transition metal compound, biscyclopentadienyl ligand, catalyst composition, and method for producing polyolefin
US20090043057A1 (en) Transition Metal Compound, Catalyst for Olefin Polymerization, and Process for Producing Olefin Polymer
TWI579293B (en) Transition metal compounds, catalyst for olefin polymerization, and olefin polymer
JP4367687B2 (en) Bridged metallocene compound for olefin polymerization and olefin polymerization method using the same
AU7758198A (en) Metallocenes and catalysts for polymerization of olefins
JP4367688B2 (en) Bridged metallocene compound for olefin polymerization and olefin polymerization method using the same
WO2006025540A1 (en) Process for producing propylene polymer
TWI396700B (en) Transition metal compound, olefin polymerization catalyst and process for producing olefin polymer
JP4367689B2 (en) Bridged metallocene compound for olefin polymerization and olefin polymerization method using the same
JP4610859B2 (en) Bridged metallocene compound for olefin polymerization and olefin polymerization method using the same
JP4111814B2 (en) Olefin polymerization method
JP2004189667A (en) Crosslinked metallocene compound for polymerization of olefin, and method for polymerizing olefin by using the same
JP2014073983A (en) Novel metallocene compound, olefin polymerization catalyst, and production process of olefin polymer
JP2010047630A (en) Preparation for high molecular weight olefin polymer
JP2019172794A (en) Method for producing olefin polymer
JP2006124452A (en) Propylene polymer